| 1. |
- Downing, Andrea S., et al.
(author)
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Coupled human and natural system dynamics as key to the sustainability of Lake Victoria's ecosystem services
- 2014
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In: Ecology and Society. - 1708-3087. ; 19:4, s. 31-
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Journal article (peer-reviewed)abstract
- East Africa's Lake Victoria provides resources and services to millions of people on the lake's shores and abroad. In particular, the lake's fisheries are an important source of protein, employment, and international economic connections for the whole region. Nonetheless, stock dynamics are poorly understood and currently unpredictable. Furthermore, fishery dynamics are intricately connected to other supporting services of the lake as well as to lakeshore societies and economies. Much research has been carried out piecemeal on different aspects of Lake Victoria's system; e.g., societies, biodiversity, fisheries, and eutrophication. However, to disentangle drivers and dynamics of change in this complex system, we need to put these pieces together and analyze the system as a whole. We did so by first building a qualitative model of the lake's social-ecological system. We then investigated the model system through a qualitative loop analysis, and finally examined effects of changes on the system state and structure. The model and its contextual analysis allowed us to investigate system-wide chain reactions resulting from disturbances. Importantly, we built a tool that can be used to analyze the cascading effects of management options and establish the requirements for their success. We found that high connectedness of the system at the exploitation level, through fisheries having multiple target stocks, can increase the stocks' vulnerability to exploitation but reduce society's vulnerability to variability in individual stocks. We describe how there are multiple pathways to any change in the system, which makes it difficult to identify the root cause of changes but also broadens the management toolkit. Also, we illustrate how nutrient enrichment is not a self-regulating process, and that explicit management is necessary to halt or reverse eutrophication. This model is simple and usable to assess system-wide effects of management policies, and can serve as a paving stone for future quantitative analyses of system dynamics at local scales.
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| 2. |
- Brant, William, et al.
(author)
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Selective Control of Composition in Prussian White for Enhanced Material Properties
- 2019
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In: Chemistry of Materials. - : AMER CHEMICAL SOC. - 0897-4756 .- 1520-5002. ; 31:18, s. 7203-7211
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Journal article (peer-reviewed)abstract
- Sodium-ion batteries based on Prussian blue analogues (PBAs) are ideal for large-scale energy storage applications due to the ability to meet the huge volumes and low costs required. For Na2-xFe[Fe(CN)(6)](1-y)center dot zH(2)O, realizing its commercial potential means fine control of the concentration of sodium, Fe(CN)(6) vacancies, and water content. To date, there is a huge variation in the literature of composition leading to variable electrochemical performance. In this work, we break down the synthesis of PBAs into three steps for controlling the sodium, vacancy, and water content via an inexpensive, scalable synthesis method. We produce rhombohedral Prussian white Na1.88(5)Fe[Fe-(CN)(6)]center dot 0.18(9)H2O with an initial capacity of 158 mAh/g retaining 90% capacity after 50 cycles. Subsequent characterization revealed that the increased polarization on the 3 V plateau is coincident with a phase transition and reduced utilization of the high-spin Fe(III)/Fe(II) redox couple. This reveals a clear target for subsequent improvements of the material to boost long-term cycling stability. These results will be of great interest for the myriad of applications of PBAs, such as catalysis, magnetism, electrochromics, and gas sorption.
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| 3. |
- Ericsson, Tore, et al.
(author)
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Investigation of Valence Mixing in Sodium-Ion Battery Cathode Material Prussian White by Mossbauer Spectroscopy
- 2022
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In: Frontiers in Energy Research. - : Frontiers Media S.A.. - 2296-598X. ; 10
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Journal article (peer-reviewed)abstract
- Prussian white (PW), Na2Fe [Fe(CN)(6)], is a highly attractive cathode material for sustainable sodium-ion batteries due to its high theoretical capacity of similar to 170 mAhg(-1) and low-cost synthesis. However, there exists significant variability in the reported electrochemical performance. This variability originates from compositional flexibility possible for all Prussian blue analogs (PBAs) and is exasperated by the difficulty of accurately quantifying the specific composition of PW. This work presents a means of accurately quantifying the vacancy content, valence distribution, and, consequently, the overall composition of PW via Mossbauer spectroscopy. PW cathode material with three different sodium contents was investigated at 295 and 90 K. The observation of only two iron environments for the fully sodiated compound indicated the absence of [Fe(CN)(6)](4-) vacancies. Due to intervalence charge transfer between iron centers at 295 K, accurate determination of valences was not possible. However, by observing the trend of spectral intensities and center shift for the nitrogen-bound and carbon-bound iron, respectively, at 90 K, valence mixing between the iron sites could be quantified. By accounting for valence mixing, the sum of iron valences agreed with the sodium content determined from elemental analysis. Without an agreement between the total valence sum and the determined composition, there exists uncertainty around the accuracy of the elemental analysis and vacancy content determination. Thus, this study offers one more stepping stone toward a more rigorous characterization of composition in PW, which will enable further optimization of properties for battery applications. More broadly, the approach is valuable for characterizing iron-based PBAs in applications where precise composition, valence determination, and control are desired.
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| 4. |
- Menon, Ashok S., et al.
(author)
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A Crystallographic Reinvestigation of Li1.2Mn0.6Ni0.2O2
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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.
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| 5. |
- Menon, Ashok S., et al.
(author)
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Influence of Synthesis Routes on the Crystallography, Morphology, and Electrochemistry of Li2MnO3
- 2020
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In: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 12:5, s. 5939-5950
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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.
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| 6. |
- Menon, Ashok S., et al.
(author)
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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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In: Dalton Transactions. - : Royal Society of Chemistry. - 1477-9226 .- 1477-9234. ; 51:11, s. 4435-4446
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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.
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| 7. |
- Menon, Ashok S., et al.
(author)
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Synthetic Pathway Determines the Nonequilibrium Crystallography of Li- and Mn-Rich Layered Oxide Cathode Materials
- 2021
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In: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 4:2, s. 1924-1935
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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.
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| 8. |
- Nielsen, Ida, et al.
(author)
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Water driven phase transitions in Prussian white cathode materials
- 2022
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In: Journal of Physics. - : Institute of Physics (IOP). - 2515-7655. ; 4:4
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Journal article (peer-reviewed)abstract
- Prussian white (PW, Na2Fe [Fe(CN)(6)] center dot zH(2)O) is a promising cathode material for use in sodium-ion batteries for large-scale energy storage applications, which demand long cycling life-times. However, for non-aqueous battery applications PW must not contain any water, and yet dehydration induces a large volume change destabilizing the structure and reducing the cycling life. The material undergoes multiple phase transitions as a function of both the sodium and water content, however, the mechanism behind is poorly understood. Here, we use neutron diffraction to explore the influence of water on the structure of PW. For the first time, two structures for a single composition of PW were observed near room temperature independent of the synthesis method. These structures differ in the FeN6 and FeC6 octahedral tilting configurations, which is connected to the ordering of water in the framework. The removal of water modulates the magnitude of pre-existing structural distortions, if it is itself disordered within the structure, rather than modifying the nature of the distortions. These results provide a robust fundamental understanding of the chemical driving force impacting the nature and magnitude of structural distortions in Prussian blue analogues. The insights provide guidance for designing tilt-engineering ultimately enabling new materials with enhanced long-term electrochemical performance in battery applications.
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| 9. |
- Ojwang, Dickson O., 1985-, et al.
(author)
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Guest water hinders sodium-ion diffusion in low-defect Berlin green cathode material
- 2022
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In: Dalton Transactions. - : Royal Society of Chemistry (RSC). - 1477-9226 .- 1477-9234. ; 51:38, s. 14712-14720
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Journal article (peer-reviewed)abstract
- Among Prussian blue analogues (PBAs), NaxFe[Fe(CN)(6)](1-y)center dot nH(2)O is a highly attractive cathode material for sodium-ion batteries due to its high theoretical capacity of similar to 170 mA h g(-1) and inexpensive raw materials. However, concerns remain over its long-term electrochemical performance and structural factors which impact sources of resistance in the material and subsequently rate performance. Refined control of the [Fe(CN)(6)] vacancies and water content could help in realizing its market potential. In this context, we have studied a low-defect Berlin green (BG) Na0.30(5)Fe[Fe(CN)(6)](0.94(2))center dot nH(2)O with varied water content corresponding to 10, 8, 6, and 2 wt%. The impact of water on the electrochemical properties of BG was systematically investigated. The electrodes were cycled within a narrow voltage window of 3.15-3.8 V vs. Na/Na+ to avoid undesired phase transitions and side reactions while preserving the cubic structure. We demonstrate that thermal dehydration leads to a significantly improved cycling stability of over 300 cycles at 15 mA g(-1) with coulombic efficiency of >99.9%. In particular, the electrode with the lowest water content exhibited the fastest Na+-ion insertion/extraction as evidenced by the larger CV peak currents during successive scans compared to hydrated samples. The results provide fundamental insight for designing PBAs as electrode materials with enhanced electrochemical performance in energy storage applications.
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| 10. |
- Ojwang, Dickson O., et al.
(author)
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Influence of sodium content on the thermal behavior of low vacancy Prussian white cathode material
- 2020
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In: Dalton Transactions. - : ROYAL SOC CHEMISTRY. - 1477-9226 .- 1477-9234. ; 49:11, s. 3570-3579
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Journal article (peer-reviewed)abstract
- Rechargeable sodium-ion batteries are the most attractive substitutes for lithium-ion batteries in large-scale energy storage devices due to wide spread reserves and low-cost of sodium resources and the similarities between sodium and lithium chemistry. However, finding a suitable cathode material is still a hurdle to be overcome. To date, Prussian white (PW), NaxFe[Fe(CN)(6)](y)center dot nH(2)O has stood out as one of the most promising Na-host materials due to its low cost, facile synthesis and competitive electrochemical capacity. Despite this, there are concerns that this material will thermally decompose at relatively low temperatures to form cyanogen gas, which is a safety hazard. Thus, low vacancy NaxFe[Fe(CN)(6)](y)center dot nH(2)O (x = 1.5, 1, 0.5 and 0) has been synthesized, and the influence of x on its thermal behavior systematically investigated. It is demonstrated that the thermal decomposition temperature, water content and moisture sensitivity of the samples strongly depend on the sodium content. The sample with x = 1.5 is found to be the most thermally stable and has the highest water content under the same experimental conditions. In addition, the sodium-rich samples (x = 1.5, 1 and 0.5) have higher surface water than the sodium-deficient one (x = 0). The local structure for this sample is also very different to the sodium-rich ones. Our findings offer new insights into the profound implications of proper material handling and safer operating conditions for practical Na-ion batteries and may be extended to analogous systems.
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