| 141. |
- Rizell, Josef, 1996, et al.
(författare)
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Neutron Reflectometry Study of Solid Electrolyte Interphase Formation in Highly Concentrated Electrolytes
- 2023
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Ingår i: Small Structures. - : WILEY. - 2688-4062. ; 4:11
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Tidskriftsartikel (refereegranskat)abstract
- Highly concentrated electrolytes have been found to improve the cycle life and Coulombic efficiency of lithium metal anodes, as well as to suppress dendrite growth. However, the mechanism for these improvements is not well understood. Partly, this can be linked to the difficulty of accurately characterizing the solid electrolyte interphase (SEI), known to play an important role for anode stability and stripping/plating efficiency. Herein, in situ neutron reflectometry is used to obtain information about SEI formation in a highly concentrated ether-based electrolyte. With neutron reflectometry, the thickness, scattering length density (SLD), and roughness of the SEI layer formed on a Cu working electrode are nondestructively probed. The reflectivity data point to the formation of a thin (5 nm) SEI in the highly concentrated electrolyte (salt:solvent ratio 1:2.2), while a considerably thicker (13 nm) SEI is formed in an electrolyte at lower salt concentration (salt:solvent ratio 1:13.7). Further, the SEI formed in the electrolyte with high salt concentration has a higher SLD, suggesting that the chemical composition of the SEI changes. The results from neutron reflectometry correlate well with the electrochemical data from SEI formation.
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| 142. |
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| 143. |
- Sadd, Matthew, 1994, et al.
(författare)
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Investigating microstructure evolution of lithium metal during plating and stripping via operando X-ray tomographic microscopy
- 2023
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Ingår i: Nature Communications. - : Springer Science and Business Media LLC. - 2041-1723 .- 2041-1723. ; 14
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Tidskriftsartikel (refereegranskat)abstract
- Efficient lithium metal stripping and plating operation capable of maintaining electronic and ionic conductivity is crucial to develop safe lithium metal batteries. However, monitoring lithium metal microstructure evolution during cell cycling is challenging. Here, we report the development of an operando synchrotron X-ray tomographic microscopy method capable of probing in real-time the formation, growth, and dissolution of Li microstructures during the cycling of a Li||Cu cell containing a standard non-aqueous liquid electrolyte solution. The analyses of the operando X-ray tomographic microscopy measurements enable tracking the evolution of deposited Li metal as a function of time and applied current density and distinguishing the formation of electrochemically inactive Li from the active bulk of Li microstructures. Furthermore, in-depth analyses of the Li microstructures shed some light on the structural connectivity of deposited Li at different current densities as well as the formation mechanism of fast-growing fractal Li microstructures, which are ultimately responsible for cell failure.
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| 144. |
- Sadd, Matthew, 1994, et al.
(författare)
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Polysulfide Speciation and Migration in Catholyte Lithium−Sulfur Cells
- 2022
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Ingår i: ChemPhysChem. - : Wiley. - 1439-7641 .- 1439-4235. ; 23:4
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Tidskriftsartikel (refereegranskat)abstract
- Semi-liquid catholyte Lithium−Sulfur (Li−S) cells have shown to be a promising path to realize high energy density energy storage devices. In general, Li−S cells rely on the conversion of elemental sulfur to soluble polysulfide species. In the case of catholyte cells, the active material is added through polysulfide species dissolved in the electrolyte. Herein, we use operando Raman spectroscopy to track the speciation and migration of polysulfides in the catholyte to shed light on the processes taking place. Combined with ex-situ surface and electrochemical analysis we show that the migration of polysulfides is central in order to maximize the performance in terms of capacity (active material utilization) as well as interphase stability on the Li-metal anode during cycling. More specifically we show that using a catholyte where the polysulfides have the dual roles of active material and conducting species, e. g. no traditional Li-salt (such as LiTFSI) is present, results in a higher mobility and faster migration of polysulfides. We also reveal how the formation of long chain polysulfides in the catholyte is delayed during charge as a result of rapid formation and migration of shorter chain species, beneficial for reaching higher capacities. However, the depletion of ionic species during the last stage of charge, due to the conversion to and precipitation of elemental sulfur on the cathode support, results in polarization of the cell before full conversion can be achieved.
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| 145. |
- Sadd, Matthew, 1994, et al.
(författare)
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Visualization of Dissolution‐Precipitation Processes in Lithium–Sulfur Batteries
- 2022
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Ingår i: Advanced Energy Materials. - : Wiley. - 1614-6840 .- 1614-6832. ; 12:10
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Tidskriftsartikel (refereegranskat)abstract
- In this work, light is shed on the dissolution and precipitation processes S8 and Li2S, and their role in the utilization of active material in Li-S batteries. Combining operando X-ray Tomographic Microscopy and optical image analysis, in real-time; sulfur conversion/dissolution in the cathode, the diffusion of polysulfides in the bulk electrolyte, and the redeposition of the product of the electrochemical reaction, Li2S, on the cathode are followed. Using a custom-designed capillary cell, positioning the entire cathode volume within the field of view, the conversion of elemental sulfur to soluble polysulfides during discharge is quantitatively followed. The results show the full utilization of elemental sulfur in the cathode in the initial stage of discharge, with all solid sulfur converted to soluble polysulfide species. Optical image analysis shows a rapid diffusion of polysulfides as they migrate from the cathode to the bulk electrolyte at the start of discharge and back to the cathode in the later stages of discharge, with the formation and precipitation of Li2S. The results point to the redeposition of Li2S on all available surfaces in the cathode forming a continuous insulating layer, leaving polysulfide species remaining in the electrolyte, and this is the process limiting the cell's specific capacity.
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| 146. |
- Schantz Zackrisson, Anna, 1973, et al.
(författare)
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Concentration effects on irreversible colloid cluster aggregation and gelation of silica dispersions.
- 2006
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Ingår i: Journal of colloid and interface science. - : Elsevier BV. - 0021-9797 .- 1095-7103. ; 301:1, s. 137-44
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Tidskriftsartikel (refereegranskat)abstract
- Effects of particle concentration on the irreversible aggregation of colloidal silica are studied using in situ destabilization via the ionic strength increase derived from the enzymatic hydrolysis of urea by urease. Aggregation is monitored by time-resolved optical density and dynamic light scattering measurements. It terminates at a gel boundary, signaled by a prominent increase of the optical density and incipient non-ergodicity. Raman scattering is used to demonstrate that the enzymatic reaction continues, well beyond gelation for the compositions studied here, until the urea is consumed. Calibration of the ionic conductivity permits for constructing stability diagrams in terms of particle and salt concentration. As with reversible gelation, the process exhibits a collective character in that lower ionic strengths are required for gelation of concentrated dispersions and vice versa. However, light scattering demonstrates that the gel boundary is preceded here by a line marking the transition from reversible to irreversible cluster formation, with the two transition boundaries tracking each other. Comparisons are made with dispersions destabilized by direct addition of salt solutions, which gel under very different conditions.
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| 147. |
- Scheers, Johan, 1979, et al.
(författare)
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Ionic liquids and oligomer electrolytes based on the B(CN)(4)(-) anion; ion association, physical and electrochemical propertiesw
- 2011
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 13:33, s. 14953-14959
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Tidskriftsartikel (refereegranskat)abstract
- The role of B(CN)(4)(-) (Bison) as a component of battery electrolytes is addressed by investigating the ionic conductivity and phase behaviour of ionic liquids (ILs), ion association mechanisms, and the electrochemical stability and cycling properties of LiBison based electrochemical cells. For C(4)mpyrBison and C(2)mimBison ILs, and mixtures thereof, high ionic conductivities (3.4
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| 148. |
- Senf, Deborah, et al.
(författare)
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Tailormade Polysaccharides with Defined Branching Patterns: Enzymatic Polymerization of Arabinoxylan Oligosaccharides
- 2018
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Ingår i: Angewandte Chemie - International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 57:37, s. 11987-11992
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Tidskriftsartikel (refereegranskat)abstract
- The heterogeneous nature of non-cellulosic polysaccharides, such as arabinoxylan, makes it difficult to correlate molecular structure with macroscopic properties. To study the impact of specific structural features of the polysaccharides on crystallinity or affinity to other cell wall components, collections of polysaccharides with defined repeating units are required. Herein, a chemoenzymatic approach to artificial arabinoxylan polysaccharides with systematically altered branching patterns is described. The polysaccharides were obtained by glycosynthase-catalyzed polymerization of glycosyl fluorides derived from arabinoxylan oligosaccharides. X-ray diffraction and adsorption experiments on cellulosic surfaces revealed that the physicochemical properties of the synthetic polysaccharides strongly depend on the specific nature of their substitution patterns. The artificial polysaccharides allow structure–property relationship studies that are not accessible by other means.
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| 149. |
- Shah, Furqan A., et al.
(författare)
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3D printed Ti6Al4V implant surface promotes bone maturation and retains a higher density of less aged osteocytes at the bone-implant interface.
- 2016
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Ingår i: Acta Biomaterialia. - : Elsevier BV. - 1878-7568 .- 1742-7061. ; 30, s. 357-367
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Tidskriftsartikel (refereegranskat)abstract
- For load-bearing orthopaedic applications, metal implants having an interconnected pore structure exhibit the potential to facilitate bone ingrowth and the possibility for reducing the stiffness mismatch between the implant and bone, thus eliminating stress-shielding effects. 3D printed solid and macro-porous Ti6Al4V implants were evaluated after six-months healing in adult sheep femora. The ultrastructural composition of the bone-implant interface was investigated using Raman spectroscopy and electron microscopy, in a correlative manner. The mineral crystallinity and the mineral-to-matrix ratios of the interfacial tissue and the native bone were found to be similar. However, lower Ca/P ratios, lower carbonate content, but higher proline, phenylalanine and tyrosine levels indicated that the interfacial tissue remained less mature. Bone healing was more advanced at the porous implant surface (vs. the solid implant surface) based on the interfacial tissue ν1 CO3(2-)/ν2 PO4(3-) ratio, phenylalanine and tyrosine levels approaching those of the native bone. The mechanosensing infrastructure in bone, the osteocyte lacuno-canalicular network, retained ∼40% more canaliculi per osteocyte lacuna, i.e., a 'less aged' morphology at the interface. The osteocyte density per mineralised surface area was ∼36-71% higher at the interface after extended healing periods.
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| 150. |
- Shah, Furqan A., et al.
(författare)
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Long-term osseointegration of 3D printed CoCr constructs with an interconnected open-pore architecture prepared by electron beam melting.
- 2016
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Ingår i: Acta Biomaterialia. - : Elsevier BV. - 1878-7568 .- 1742-7061. ; 36:May, s. 296-309
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Tidskriftsartikel (refereegranskat)abstract
- In orthopaedic surgery, cobalt chromium (CoCr) based alloys are used extensively for their high strength and wear properties, but with concerns over stress shielding and bone resorption due to the high stiffness of CoCr. The structural stiffness, principally related to the bulk and the elastic modulus of the material, may be lowered by appropriate design modifications, to reduce the stiffness mismatch between metal/alloy implants and the adjacent bone. Here, 3D printed CoCr and Ti6Al4V implants of similar macro-geometry and interconnected open-pore architecture prepared by electron beam melting (EBM) were evaluated following 26week implantation in adult sheep femora. Despite higher total bone-implant contact for Ti6Al4V (39±4%) than CoCr (27±4%), bone formation patterns were similar, e.g., densification around the implant, and gradual ingrowth into the porous network, with more bone in the outer half (periphery) than the inner half (centre). Raman spectroscopy revealed no major differences in mineral crystallinity, the apatite-to-collagen ratio, or the carbonate-to-phosphate ratio. Energy dispersive X-ray spectroscopy showed similar Ca/P ratio of the interfacial tissue adjacent to both materials. Osteocytes made direct contact with CoCr and Ti6Al4V. While osteocyte density and distribution in the new-formed bone were largely similar for the two alloys, higher osteocyte density was observed at the periphery of the porous network for CoCr, attributable to slower remodelling and a different biomechanical environment. The results demonstrate the possibility to achieve bone ingrowth into open-pore CoCr constructs, and attest to the potential for fabricating customised osseointegrated CoCr implants for load-bearing applications.
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