| 1. |
- Agostini, Marco, 1987, et al.
(författare)
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A high-power and fast charging Li-ion battery with outstanding cycle-life
- 2017
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Ingår i: Scientific Reports. - : Springer Science and Business Media LLC. - 2045-2322 .- 2045-2322. ; 7:1
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Tidskriftsartikel (refereegranskat)abstract
- Electrochemical energy storage devices based on Li-ion cells currently power almost all electronic devices and power tools. The development of new Li-ion cell configurations by incorporating innovative functional components (electrode materials and electrolyte formulations) will allow to bring this technology beyond mobile electronics and to boost performance largely beyond the state-of-theart. Here we demonstrate a new full Li-ion cell constituted by a high-potential cathode material, i.e. LiNi0.5Mn1.5O4, a safe nanostructured anode material, i.e. TiO2, and a composite electrolyte made by a mixture of an ionic liquid suitable for high potential applications, i.e. Pyr(1),4PF6, a lithium salt, i.e. LiPF6, and standard organic carbonates. The final cell configuration is able to reversibly cycle lithium for thousands of cycles at 1000 mAg(-1) and a capacity retention of 65% at cycle 2000.
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| 2. |
- Agostini, Marco, 1987, et al.
(författare)
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A mixed mechanochemical-ceramic solid-state synthesis as simple and cost effective route to high-performance LiNi0.5Mn1.5O4 spinels
- 2017
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Ingår i: Electrochimica Acta. - : Elsevier BV. - 0013-4686. ; 235, s. 262-269
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Tidskriftsartikel (refereegranskat)abstract
- The implementation of high potential materials as positive electrodes in high energy Li-ion batteries requires to develop scalable and smart synthetic routes. In the case of the LiNi0.5Mn1.5O4 (LNMO) spinel material, a successful preparation strategy must drive the phase formation in order to obtain structural, morphological and surface properties capable to boost performances in lithium cells and minimize the electrolyte degradation. Here we discuss a novel simple and easily scalable mechanochemical synthetic route, followed by a high temperature annealing in air, to prepare LMNO materials starting from oxides. A synergic doping with chromium and iron has been incorporated, resulting in the spontaneous segregation of a CrOx-rich surface layer. The effect of the annealing temperature on the physico-chemical properties of the LMNO material has been investigated as well as the effect on the performances in Licells.
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| 3. |
- Agostini, Marco, 1987, et al.
(författare)
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Designing a Safe Electrolyte Enabling Long‐Life Li/S Batteries
- 2019
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 12:18, s. 4176-4184
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Tidskriftsartikel (refereegranskat)abstract
- Lithium–sulfur (Li/S) batteries suffer from “shuttle” reactions in which soluble polysulfide species continuously migrate to and from the Li metal anode. As a consequence, the loss of active material and reactions at the surface of Li limit the practical applications of Li/S batteries. LiNO3 has been proposed as an electrolyte additive to reduce the shuttle reactions by aiding the formation of a stable solid electrolyte interphase (SEI) at the Li metal, limiting polysulfide shuttling. However, LiNO3 is continuously consumed during cycling, especially at low current rates. Therefore, the Li/S battery cycle life is limited by the LiNO3 concentration in the electrolyte. In this work, an ionic liquid (IL) [N-methyl-(n-butyl)pyrrolidinium bis(trifluoromethylsulfonyl)imide] was used as an additive to enable longer cycle life of Li/S batteries. By tuning the IL concentration, an enhanced stability of the SEI and lower flammability of the solutions were demonstrated, that is, higher safety of the battery. The Li/S cell built with a high sulfur mass loading (4 mg cm−2) and containing the IL-based electrolyte demonstrated a stable capacity of 600 mAh g−1 for more than double the number of cycles of a cell containing LiNO3 additive.
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| 4. |
- Agostini, Marco, 1987, et al.
(författare)
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Designing Highly Conductive Functional Groups Improving Guest-Host Interactions in Li/S Batteries
- 2020
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Ingår i: Small. - : Wiley. - 1613-6810 .- 1613-6829. ; 16:2
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Tidskriftsartikel (refereegranskat)abstract
- Li-sulfur batteries are of great interest due to their potential to surpass the energy densities of other battery types, but the low electronic conductivity of both sulfur and its discharge products requires the use of a conductive host material. The most common is the use of different porous carbons which normally are hydrophobic and hardly retain the polar discharge products of the Li/S reaction, such as Li2S and lithium polysulfides (LiPs), at the working electrode. Functionalized hosts have been proposed as a strategy to improve LiPs interactions, including the use of heteroatom doping, organic frameworks, metals, metal oxides, sulfide particles, and conductive polymers. Despite demonstrating an improved cycle life, the functionalized structures often have an intrinsic limitation related to a low electronic conductivity resulting in slow kinetics and poor rate capability of Li/S cells. Herein, recent research trends aimed at designing sulfur electrodes with highly conductive functional groups on nanostructured hosts surface are reviewed. The main concepts, key developments, and parameters for building 3D hosts architectures that enable fast charge rates and long cycle life at high sulfur loadings are discussed.
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| 5. |
- Agostini, Marco, 1987, et al.
(författare)
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Free-Standing 3D-Sponged Nanofiber Electrodes for Ultrahigh-Rate Energy-Storage Devices
- 2018
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Ingår i: ACS Applied Materials & Interfaces. - : American Chemical Society (ACS). - 1944-8252 .- 1944-8244. ; 10:40, s. 34140-34146
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Tidskriftsartikel (refereegranskat)abstract
- We have designed a self-standing anode built-up from highly conductive 3D-sponged nanofibers, that is, with no current collectors, binders, or additional conductive agents. The small diameter of the fibers combined with an internal spongelike porosity results in short distances for lithium-ion diffusion and 3D pathways that facilitate the electronic conduction. Moreover, functional groups at the fiber surfaces lead to the formation of a stable solid-electrolyte interphase. We demonstrate that this anode enables the operation of Li-cells at specific currents as high as 20 A g-1 (approx. 50C) with excellent cycling stability and an energy density which is >50% higher than what is obtained with a commercial graphite anode.
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| 6. |
- Agostini, Marco, 1987, et al.
(författare)
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Minimizing the Electrolyte Volume in Li–S Batteries: A Step Forward to High Gravimetric Energy Density
- 2018
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Ingår i: Advanced Energy Materials. - : Wiley. - 1614-6840 .- 1614-6832. ; 8:26
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Tidskriftsartikel (refereegranskat)abstract
- Sulfur electrodes confined in an inert carbon matrix show practical limitations and concerns related to low cathode density. As a result, these electrodes require a large amount of electrolyte, normally three times more than the volume used in commercial Li-ion batteries. Herein, a high-energy and high-performance lithium–sulfur battery concept, designed to achieve high practical capacity with minimum volume of electrolyte is proposed. It is based on deposition of polysulfide species on a self-standing and highly conductive carbon nanofiber network, thus eliminating the need for a binder and current collector, resulting in high active material loading. The fiber network has a functionalized surface with the presence of polar oxygen groups, with the aim to prevent polysulfide migration to the lithium anode during the electrochemical process, by the formation of S–O species. Owing to the high sulfur loading (6 mg cm−2) and a reduced free volume of the sulfide/fiber electrode, the Li–S cell is designed to work with as little as 10 µL cm−2of electrolyte. With this design the cell has a high energy density of 450 Wh kg−1, a lifetime of more than 400 cycles, and the possibility of low cost, by use of abundant and eco-friendly materials.
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| 7. |
- Agostini, M., et al.
(författare)
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Polysulfide-containing Glyme-based Electrolytes for Lithium Sulfur Battery
- 2015
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Ingår i: Chemistry of Materials. - : American Chemical Society (ACS). - 1520-5002 .- 0897-4756. ; 27:13, s. 4604-4611
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Tidskriftsartikel (refereegranskat)abstract
- A new comparative investigation of lithium sulfur cells employing a tetraethylene glycol dimethyl ether-lithium trifluoromethanesulfonate (TEGDME-LiCF3SO3) electrolyte charged by various polysulfide species (Li2S2, Li2S4, Li2S6, and Li2S8) is here reported. We carefully detect the effects of lithium polysulfide addition by originally combining X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). The measurements clearly reveal how the polysulfide addition affects the nature and composition of the solid electrolyte interphase (SEI) in terms of precipitated S-based species determined by XPS. The study demonstrates that the SEI layer formed on the Li anode decreases in impedance and stabilizes by the presence of polysulfide. This, together with a buffer effect strongly mitigating the sulfur-cathode dissolution and the shuttle reaction, significantly improves the stability of the lithium-sulfur cell. The data here reported clearly suggest the polysulfide as an effective additive to enhance the performance of the lithium-sulfur battery (Graph Presented).
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| 8. |
- Agostini, Marco, 1987, et al.
(författare)
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Rational Design of Low Cost and High Energy Lithium Batteries through Tailored Fluorine-free Electrolyte and Nanostructured S/C Composite
- 2018
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 11:17, s. 2981-2986
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Tidskriftsartikel (refereegranskat)abstract
- We report a new Li–S cell concept based on an optimized F-free catholyte solution and a high loading nanostructured C/S composite cathode. The Li2S8present in the electrolyte ensures both buffering against active material dissolution and Li+conduction. The high S loading is obtained by confining elemental S (≈80 %) in the pores of a highly ordered mesopores carbon (CMK3). With this concept we demonstrate stabilization of a high energy density and excellent cycling performance over 500 cycles. This Li–S cell has a specific capacity that reaches over 1000 mA h g−1, with an overall S loading of 3.6 mg cm−2and low electrolyte volume (i.e., 10 μL cm−2), resulting in a practical energy density of 365 Wh kg−1. The Li–S system proposed thus meets the requirements for large scale energy storage systems and is expected to be environmentally friendly and have lower cost compared with the commercial Li-ion battery thanks to the removal of both Co and F from the overall formulation.
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| 9. |
- Agostini, Marco, 1987, et al.
(författare)
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Stabilizing the Performance of High-Capacity Sulfur Composite Electrodes by a New Gel Polymer Electrolyte Configuration
- 2017
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Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 10:17, s. 3490-3496
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Tidskriftsartikel (refereegranskat)abstract
- Increased pollution and the resulting increase in global warming are drawing attention to boosting the use of renewable energy sources such as solar or wind. However, the production of energy from most renewable sources is intermittent and thus relies on the availability of electrical energy-storage systems with high capacity and at competitive cost. Lithium–sulfur batteries are among the most promising technologies in this respect due to a very high theoretical energy density (1675 mAh g?1) and that the active material, sulfur, is abundant and inexpensive. However, a so far limited practical energy density, life time, and the scaleup of materials and production processes prevent their introduction into commercial applications. In this work, we report on a simple strategy to address these issues by using a new gel polymer electrolyte (GPE) that enables stable performance close to the theoretical capacity of a low cost sulfur–carbon composite with high loading of active material, that is, 70 % sulfur. We show that the GPE prevents sulfur dissolution and reduces migration of polysulfide species to the anode. This functional mechanism of the GPE membranes is revealed by investigating both its morphology and the Li-anode/GPE interface at various states of discharge/charge using Raman spectroscopy.
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| 10. |
- Aguilera Medina, Luis, 1983, et al.
(författare)
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A structural study of LiTFSI-tetraglyme mixtures: From diluted solutions to solvated ionic liquids
- 2015
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Ingår i: Journal of Molecular Liquids. - : Elsevier BV. - 0167-7322. ; 210:Part B, s. 238-242
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Tidskriftsartikel (refereegranskat)abstract
- We report on the nano-structure of solvated ionic liquids (SILs) formed by dissolving a Li-salt (LiTFSI) in the solvent tetraglyme. Using small angle X-ray scattering (SAXS), supported by Raman spectroscopy and computational modeling we follow how the nano-structure develops as Li-salt is added to the solvent. We find that, as the Li-salt concentration is increased a peak at Q 0.95 Å- 1 grows in intensity, signaling the presence of structural correlations typical of those found in traditional ionic liquids. The intensity of the peak reaches its maximum at the equimolar concentration, where each Li-ion can be solvated by one solvent molecule forming an effective cation complex. Combining the SAXS data with computer modeling we show that this peak can be assigned to charge alternation, also found in traditional ionic liquids. However, we also show that even at the equimolar concentration not all Li-ions are solvated by the solvent molecules, but a small fraction interacts directly with the anion (TFSI).
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| 11. |
- Aguilera Medina, Luis, 1983, et al.
(författare)
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Enhanced low-temperature ionic conductivity via different Li+ solvated clusters in organic solvent/ionic liquid mixed electrolytes
- 2016
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 18:36, s. 25458-25464
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Tidskriftsartikel (refereegranskat)abstract
- We investigate Li+ coordination in mixed electrolytes based on ionic liquids (ILs) and organic solvents and its relation with the macroscopic properties such as phase behaviour and ionic conductivity. Using Raman spectroscopy we determine the solvation shell around Li+ in mixtures formed by the IL N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide, the organic solvents ethylene carbonate and dimethyl carbonate (EC : DMC 1 : 1), and the salt LiTFSI. We find that the organic solvent molecules preferentially solvate Li+ as long as there are enough of them. Our results are consistent with a model where Li(EC)(3)(DMC)(1) and Li(EC)(2)(DMC)(2) are the main complexes formed by the organic solvent molecules and where TFSI- mainly participates in Li(TFSI)(2)(-) clusters. As the amount of organic solvent is increased, the number of TFSI- around Li+ rapidly decreases showing a higher affinity of the organic solvents to solvate Li+. The changes in the local configurations are also reflected in the ionic conductivity and the phase behaviour. The formation of larger clusters leads to a decrease in the conductivity, whereas the presence of several different clusters at intermediate compositions effectively hinders crystallization at low temperatures. The result is an enhanced low-temperature ionic conductivity in comparison with the pure IL or organic solvent electrolytes.
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| 12. |
- Aguilera Medina, Luis, 1983, et al.
(författare)
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The effect of lithium salt doping on the nanostructure of ionic liquids
- 2015
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 17:40, s. 27082-27087
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Tidskriftsartikel (refereegranskat)abstract
- In this work we report on the evolution of the structure of two model ionic liquid families, N-alkyl-N-methylpyrrolidinium (Pyr1n-TFSI) and 1-alkyl-3-methylimidazolium (CnMIm-TFSI) (n = 3, 4, 6 and 8) both containing the bis(trifluoromethanesulfonyl)imide (TFSI) anion, upon the addition of LiTFSI using small angle X-ray scattering (SAXS). The introduction of a lithium salt (Li-salt) tunes the interactions through the substitution of the large cation in the ionic liquid with the small and charge localized lithium ion, thus increasing the coulombic contribution from ion-ion interactions. We find that the introduction of lithium ions results in a restructuring of the polar groups in the ionic liquids. These changes are manifested as an increase in the correlation lengths related to charge alternation of the ions and a more disordered structure. This restructuring is interpreted as a reconfiguration of the anions as they coordinate to the small and ionic lithium. In contrast, the length scale of the mesoscopic heterogeneities related to the clustering of alkyl chains is virtually unchanged with lithium doping. Moreover, the correlation corresponding to alkyl chain domains becomes more well defined with increasing salt concentration, suggesting that Li-salt doping, i.e. an increased columbic interaction in the system, promotes clustering of the alkyl tails.
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| 13. |
- Ahmed, Istaq, 1972, et al.
(författare)
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Crystal structure and proton conductivity of BaZr0.9Sc0
- 2008
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Ingår i: Journal of the American Ceramic Society. - : Wiley. - 0002-7820 .- 1551-2916. ; 91:9, s. 3039-3044
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Tidskriftsartikel (refereegranskat)abstract
- Solid-state sintering has been used to prepare the perovskite BaZr0.9Sc0.1O3-delta. Analysis of X-ray powder diffraction data shows that an increase of the unit cell parameter, a, was observed after deuteration. Rietveld analysis of room-temperature neutron powder diffraction data confirmed cubic symmetry (space group Pm-3m). Dynamic thermogravimetric analysis indicates that the hydration process occurs below 335 degrees C and approximately 58% of the theoretical number of protonic defects can be filled. The presence of protons/deutrons is seen from the strong O-H/O-D stretch band in the infrared spectrum of the hydrated/deuterated samples. The proton conductivity of a prehydrated sample was investigated under dry and wet Ar atmospheres
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| 14. |
- Ahmed, Istaq, 1972, et al.
(författare)
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Location of deuteron sites in the proton conducting perovskite BaZr0.50In0.50O3-y
- 2008
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Ingår i: Journal of Alloys and Compounds. - : Elsevier BV. - 0925-8388. ; 450:1-2, s. 103-110
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Tidskriftsartikel (refereegranskat)abstract
- High-resolution neutron powder diffraction data have been collected on deuterated and dried samples of the perovskite BaZr0.5In0.5O2.75 at 5 K and room temperature, respectively. Inspection of Fourier nuclear density maps for the deuterated phase have allowed the deuteron position to be refined on a 12h (1/2, y, 0) crystallographic site, with y = 0.217(4) yielding a chemically reasonable O-D distance of 0.92(2) angstrom. Evidence for anisotropy of the deuteron position is also found consistent with a 24k crystallographic site (0.56, 0.21, 0) indicative of displacements of the ion towards neighbouring oxygen ions. The presence of static oxygen disorder in both the dried and deuterated samples is apparent from the structural analyses. Raman spectra confirm short range deviations from cubic symmetry for both dried and hydrated samples.
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| 15. |
- Ahmed, Istaq, 1972, et al.
(författare)
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Proton conduction in Perovskite Oxide BaZr0.5Yb0.5O3-δ Prepared by Wet Chemical Route
- 2008
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Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 1945-7111 .- 0013-4651. ; 155:11, s. 97-102
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Tidskriftsartikel (refereegranskat)abstract
- A wet chemical route has been used to synthesize the oxygen deficient perovskite Ba Zr0.5 Yb0.5 O3-δ. Analysis of X-ray powder diffraction data showed that both dried and hydrated samples adopt cubic crystal structures of space group Pm 3- m. Dynamic thermogravimetric analysis showed a significant mass loss for the hydrated sample compared to the dried sample, indicating that ∼28% of the oxygen vacancies are filled by protonic defects. The strong O-H stretch band, 2500-3500 cm-1, in the IR absorbance spectrum also clearly manifests the presence of significant levels of protons in the hydrated material. Proton conductivity was investigated on prehydrated (under dry Ar) and as-prepared (under wet Ar) samples. The heating cycle of the prehydrated sample showed higher proton conductivity compared to the cooling cycle, especially in the intermediate temperature range (150-550°C). Finally, comparison with data for Ba Zr0.9 Yb0.1 O3-δ revealed that the more heavily doped sample showed higher proton conductivity compared to the more lightly doped sample. © 2008 The Electrochemical Society.
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| 16. |
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| 17. |
- Ahmed, Istaq, 1972, et al.
(författare)
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Structural study and proton conductivity in Yb-doped BaZrO3
- 2007
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Ingår i: Solid State Ionics. - 0167-2738. ; 178:(7-10), s. 515-520
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Tidskriftsartikel (refereegranskat)abstract
- Traditional solid state sintering has been used to prepare the perovskite BaZr0.9Yb0.1O3-delta. Analysis of X-ray powder diffraction data shows that an increase of the unit cell parameter, a, was observed compared to undoped BaZrO3. Rietveld analysis of room temperature neutron powder diffraction data confirmed cubic symmetry (space group Pm-3m). Dynamic thermogravimetric analysis (TGA) indicates that the hydration process occurs below 200 degrees C. The strong O-H stretch band, 2500-3500 cm(-1), in the infrared absorbance spectrum clearly manifests the presence of protons in the hydrated material. Proton conductivity was investigated on hydrated and as-prepared samples under dry and wet atmospheres, respectively. Keywords: X-ray diffraction; neutron diffraction; Rietveld refinement; proton conductor; perovskite
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| 18. |
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| 19. |
- Ahmed, Istaq, 1972, et al.
(författare)
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Synthesis and structural characterization of perovskite type proton conducting BaZr1-xInxO3-delta (0.0 <= x <= 0.75)
- 2006
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Ingår i: Solid State Ionics. - : Elsevier BV. - 0167-2738 .- 1872-7689. ; 177:17-18, s. 1395-1403
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Tidskriftsartikel (refereegranskat)abstract
- Solid state sintering has been used to prepare the cubic perovskite structured compounds BaZr1-xInxO3-delta (0.0 <= x <= 0.75). Analysis of X-ray powder diffraction (XRPD) data reveals that the unit cell parameter, a, increases linearly with an increased Indium concentration. XRPD data was also used to demonstrate the completion of sample hydration, which was reached when the materials showed a set of single-phase Bragg-peaks. Dynamic thermogravimetric analysis (TGA) data showed that approx. 89% of the total number of available oxygen vacancies can be filled in BaZr1-xInxO3-delta for x=0.50, and that the maximum water uptake occurs below 300 degrees C. Rietveld analysis of the room temperature neutron powder diffraction (NPD) data confirmed the average cubic symmetry (space group Pm-3m), and an expansion of the unit cell parameter after the hydration reaction. The strong O-H stretch band, 2500-3500 cm(-1), in the infrared absorbance spectrum clearly manifests the presence of protons in the hydrated material. Proton conductivity of hydrated BaZr1-xInxO3-delta, x=0.75 was investigated during heating and cooling cycles under dry argon atmosphere. The total conductivity during the heating cycle was nearly two orders of magnitude greater than that of cooling cycle at 300 degrees C, whilst these values were similar at higher temperatures i.e. T > 600 degrees C.
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| 20. |
- Atkins, Duncan, et al.
(författare)
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Accelerating Battery Characterization Using Neutron and Synchrotron Techniques: Toward a Multi-Modal and Multi-Scale Standardized Experimental Workflow
- 2022
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Ingår i: Advanced Energy Materials. - : Wiley. - 1614-6840 .- 1614-6832. ; 12:17
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Tidskriftsartikel (refereegranskat)abstract
- Li-ion batteries are the essential energy-storage building blocks of modern society. However, producing ultra-high electrochemical performance in safe and sustainable batteries for example, e-mobility, and portable and stationary applications, demands overcoming major technological challenges. Materials engineering and new chemistries are key aspects to achieving this objective, intimately linked to the use of advanced characterization techniques. In particular, operando investigations are currently attracting enormous interest. Synchrotron- and neutron-based bulk techniques are increasingly employed as they provide unique insights into the chemical, morphological, and structural changes inside electrodes and electrolytes across multiple length scales with high time/spatial resolutions. However, data acquisition, data analysis, and scientific outcomes must be accelerated to increase the overall benefits to the academic and industrial communities, requiring a paradigm shift beyond traditional single-shot, sophisticated experiments. Here a multi-scale and multi-technique integrated workflow is presented to enhance bulk characterization, based on standardized and automated data acquisition and analysis for high-throughput and high-fidelity experiments, the optimization of versatile and tunable cells, as well as multi-modal correlative characterization. Furthermore, new mechanisms, methods and organizations such as artificial intelligence-aided modeling-driven strategies, coordinated beamtime allocations, and community-unified infrastructures are discussed in order to highlight perspectives in battery research at large scale facilities.
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| 21. |
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| 22. |
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| 23. |
- Brige, Amandine, et al.
(författare)
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A comparative study of hydroxyethylcellulose-based solid polymer electrolytes for solid state Zn batteries
- 2023
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Ingår i: NANO SELECT. - : Wiley. - 2688-4011. ; 4:1, s. 102-111
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Tidskriftsartikel (refereegranskat)abstract
- Rechargeable zinc metal batteries are greener and safer alternative to lithium batteries, but they suffer from poor reversibility due to growth of zinc dendrites and water splitting reactions of aqueous electrolytes. One strategy to overcome these drawbacks is replacing aqueous electrolyte with solid polymer electrolyte (SPE). In this work, we examine the possibility of fabricating solid electrolyte from a bio-based polymer, hydroxyethylcellulose (HEC), with the aim to further increase the sustainability of zinc batteries. Various types of zinc salts, drying procedures and the salt concentrations are investigated for their impact on the ionic conductivity, structure, and phase behavior of as-prepared polymer electrolytes. It is found that HEC has a good film-forming ability compared with commonly used poly(ethylene oxide) but its low salt-dissociation capability leads to an ionic conductivity of 10(-6) S cm(-1) even at the elevated temperature of 110 degrees C, hindering the possibility of solely utilizing HEC as matrix of solid electrolyte. Our results suggest that introducing a new polymer with higher salt-dissociation capability or lower glass transition temperature into the HEC matrix can be a reliable way to build solid polymer electrolytes with sufficient ionic conductivity and good mechanical property for future zinc batteries.
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| 24. |
- Calcagno, Giulio, 1990, et al.
(författare)
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Effect of Nitrogen Doping on the Performance of Mesoporous CMK-8 Carbon Anodes for Li-Ion Batteries
- 2020
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Ingår i: Energies. - : MDPI AG. - 1996-1073 .- 1996-1073. ; 13:19
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Tidskriftsartikel (refereegranskat)abstract
- Designing carbonaceous materials with heightened attention to the structural properties such as porosity, and to the functionalization of the surface, is a growing topic in the lithium-ion batteries (LIBs) field. Using a mesoporous silica KIT-6 hard template, mesoporous carbons belonging to the OMCs (ordered mesoporous carbons) family, namely 3D cubic CMK-8 and N-CMK-8 were synthesized and thoroughly structurally characterized. XPS analysis confirmed the successful introduction of nitrogen, highlighting the nature of the different nitrogen atoms incorporated in the structure. The work aims at evaluating the electrochemical performance of N-doped ordered mesoporous carbons as an anode in LIBs, underlining the effect of the nitrogen functionalization. The N-CMK-8 electrode reveals higher reversible capacity, better cycling stability, and rate capability, as compared to the CMK-8 electrode. Coupling the 3D channel network with the functional N-doping increased the reversible capacity to similar to 1000 mAh center dot g(-1) for the N-CMK-8 from similar to 450 mAh center dot g(-1) for the undoped CMK-8 electrode. A full Li-ion cell was built using N-CMK-8 as an anode, commercial LiFePO4, a cathode, and LP30 commercial electrolyte, showing stable performance for 100 cycles. The combination of nitrogen functionalization and ordered porosity is promising for the development of high performing functional anodes.
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| 25. |
- Calcagno, Giulio, 1990, et al.
(författare)
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Fast charging negative electrodes based on anatase titanium dioxide beads for highly stable Li-ion capacitors
- 2020
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Ingår i: Materials Today Energy. - : Elsevier BV. - 2468-6069. ; 16
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Tidskriftsartikel (refereegranskat)abstract
- Hybrid energy storage systems aim to achieve both high power and energy densities by combining supercapacitor-type and battery-type electrodes in tandem. The challenge is to find sustainable materials as fast charging negative electrodes, which are characterized by high capacity retention. In this study, mesoporous anatase beads are synthetized with tailored morphology to exploit fast surface redox reactions. The TiO2-based electrodes are properly paired with a commercial activated carbon cathode to form a Li-ion capacitor. The titania electrode exhibits high capacity and rate performance. The device shows extremely stable performance with an energy density of 27 mWh g-1 at a specific current of 2.5 A g−1 for 10,000 cycles. The remarkable stability is associated with a gradual shift of the potential during cycling as result of the formation of cubic LiTiO2 on the surface of the beads. This phenomenon renews the interest in using TiO2 as negative electrode for Li-ion capacitors.
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| 26. |
- Caponi, S., et al.
(författare)
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The Debye-Waller factor approaching the glass-transition temperature in phosphate glasses
- 2006
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Ingår i: Journal of Non-Crystalline Solids. - : Elsevier BV. - 0022-3093. ; 352:42-49 SPEC. ISS., s. 4577-4582
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Tidskriftsartikel (refereegranskat)abstract
- The temperature dependence of the mean square displacement, 〈u2〉, calculated by elastic neutron scattering for two phosphate glasses, (AgI)x(AgPO3)1-x with x = 0.3, 0.55, is analysed. The studied samples are probed in a wide range of temperatures going from a few tens of K up to the glass transition temperature and well into the undercooled liquid state. In the low temperature regime a solid like behaviour appears, showing a linear temperature dependence of the Debye-Waller factor, while around Tg the onset of a pronounced increase of 〈u2〉 is observed. The temperature dependence of the normalized elastic intensity and the drawn out Debye-Waller factor are fitted and analyzed by the theoretical previsions of Mode Coupling Theory finding a good agreement. © 2006 Elsevier B.V. All rights reserved.
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| 27. |
- Cavallo, Carmen, 1986, et al.
(författare)
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A free-standing reduced graphene oxide aerogel as supporting electrode in a fluorine-free Li2S8 catholyte Li-S battery
- 2019
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Ingår i: Journal of Power Sources. - : Elsevier BV. - 0378-7753. ; 416, s. 111-117
-
Tidskriftsartikel (refereegranskat)abstract
- We report on a novel, simple, and environmentally benign synthesis route for a free-standing reduced graphene oxide (r-GO) aerogel and its application as supporting electrode for the electrochemical redox reaction of sulphur in a catholyte-based lithium-sulphur battery. A mesoporous matrix is formed by a layers of r-GO, providing sites for electrochemical reactions and a highly conducting pathway for electrons. The highly porous structure is easily infiltrated by a catholyte solution providing a homogeneous distribution of the sulphur active material in the conductive graphene matrix and ensuring efficient electrochemical reactions. This is demonstrated by a high capacity, 3.4 mAh cm−2, at high mass loading, 3.2 mg cm−2 of sulphur in the cathode and in total the sulphur loading in the Li-S cell is even double (6.4 mg cm−2). Additionally, the presence of oxygen groups in the r-GO aerogel structure stabilizes the cycling performance and the Li-S cell with the fluorine free catholyte shows a capacity retention of 85% after 350 cycles.
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| 28. |
- Cavallo, Carmen, 1986, et al.
(författare)
-
Effect of the Niobium Doping Concentration on the Charge Storage Mechanism of Mesoporous Anatase Beads as an Anode for High-Rate Li-Ion Batteries
- 2021
-
Ingår i: ACS Applied Energy Materials. - : American Chemical Society (ACS). - 2574-0962. ; 4:1, s. 215-225
-
Tidskriftsartikel (refereegranskat)abstract
- A promising strategy to improve the rate performance of Li-ion batteries is to enhance and facilitate the insertion of Li ions into nanostructured oxides like TiO2. In this work, we present a systematic study of pentavalent-doped anatase TiO2 materials for third-generation high-rate Li-ion batteries. Mesoporous niobium-doped anatase beads (Nb-doped TiO2) with different Nb5+ doping (n-type) concentrations (0.1, 1.0, and 10% at.) were synthesized via an improved template approach followed by hydrothermal treatment. The formation of intrinsic n-type defects and oxygen vacancies under RT conditions gives rise to a metallic-type conduction due to a shift of the Fermi energy level. The increase in the metallic character, confirmed by electrochemical impedance spectroscopy, enhances the performance of the anatase bead electrodes in terms of rate capability and provides higher capacities both at low and fast charging rates. The experimental data were supported by density functional theory (DFT) calculations showing how a different n-type doping can be correlated to the same electrochemical effect on the final device. The Nb-doped TiO2 electrode materials exhibit an improved cycling stability at all the doping concentrations by overcoming the capacity fade shown in the case of pure TiO2 beads. The 0.1% Nb-doped TiO2-based electrodes exhibit the highest reversible capacities of 180 mAh g-1 at 1C (330 mA g-1) after 500 cycles and 110 mAh g-1 at 10C (3300 mA g-1) after 1000 cycles. Our experimental and computational results highlight the possibility of using n-type doped TiO2 materials as anodes in high-rate Li-ion batteries.
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| 29. |
- Celeste, Arcangelo, et al.
(författare)
-
Enhancement of Functional Properties of Liquid Electrolytes for Lithium-Ion Batteries by Addition of Pyrrolidinium-Based Ionic Liquids with Long Alkyl-Chains
- 2020
-
Ingår i: Batteries and Supercaps. - : Wiley. - 2566-6223. ; 3:10, s. 1059-1068
-
Tidskriftsartikel (refereegranskat)abstract
- Three ionic liquid belonging to the N-alkyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imides (Pyr(1),nTFSI with n=4,5,8) have been added as co-solvent to two commonly used electrolytes for Li-ion cells: (a) 1 M lithium hexafluorophosphate (LiPF6) in a mixture of ethylene carbonate (EC) and linear like dimethyl carbonate (DMC) in 1 : 1 v/v and (b) 1 M lithium bis-(trifluoromethanesulfonyl)imide (LiTFSI) in EC : DMC 1 : 1 v/v. These electrolyte formulations (classified as P and T series containing LiPF6 or LiTFSI salts, respectively) have been analyzed by comparing ionic conductivities, transport numbers, viscosities, electrochemical stability as well as vibrational properties. In the case of the Pyr(1,5)TFSI and Pyr(1,8)TFSI blended formulations, this is the first ever reported detailed study of their functional properties in Li-ion cells electrolytes. Overall, P-electrolytes demonstrate enhanced properties compared to the T-ones. Among the various P electrolytes those containing Pyr(1,4)TFSI and Pyr(1,5)TFSI limit the accumulation of irreversible capacity upon cycling with satisfactory performance in lithium cells.
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| 30. |
- Cengiz, Elif Ceylan, 1986, et al.
(författare)
-
Review - Reference Electrodes in Li-Ion and Next Generation Batteries: Correct Potential Assessment, Applications and Practices
- 2021
-
Ingår i: Journal of the Electrochemical Society. - : The Electrochemical Society. - 1945-7111 .- 0013-4651. ; 168:12
-
Forskningsöversikt (refereegranskat)abstract
- This review provides an accessible analysis of the processes on reference electrodes and their applications in Li-ion and next generation batteries research. It covers fundamentals and definitions as well as specific practical applications and is intended to be comprehensible for researchers in the battery field with diverse backgrounds. It covers fundamental concepts, such as two- and three-electrodes configurations, as well as more complex quasi- or pseudo- reference electrodes. The electrode potential and its dependance on the concentration of species and nature of solvents are explained in detail and supported by relevant examples. The solvent, in particular the cation solvation energy, contribution to the electrode potential is important and a largely unknown issue in most the battery research. This effect can be as high as half a volt for the Li/Li+ couple and we provide concrete examples of the battery systems where this effect must be taken into account. With this review, we aim to provide guidelines for the use and assessment of reference electrodes in the Li-ion and next generation batteries research that are comprehensive and accessible to an audience with a diverse scientific background.
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| 31. |
- Dussauze, M., et al.
(författare)
-
Lithium Ion Conducting Boron-Oxynitride Amorphous Thin Films: Synthesis and Molecular Structure by Infrared Spectroscopy and Density Functional Theory Modeling
- 2013
-
Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 117:14, s. 7202-7213
-
Tidskriftsartikel (refereegranskat)abstract
- Li ion containing oxynitride amorphous thin films are promising materials for electrochemical applications due to their high ionic conductivity, mechanical stability and chemical durability. Here we report on the preparation of Li boron-oxynitride (LiBON) amorphous thin films by rf sputtering of Li-diborate and Li-pyroborate targets in nitrogen atmosphere. The materials produced were subsequently studied by infrared transmittance spectroscopy assisted by density functional theory calculations using representative Li boron-oxide and boron-oxynitride clusters. The combination of experiments and calculations allows us to propose accurate vibrational assignments and to clarify the complex infrared activity of the LiBON films. Both experimental and calculated spectra show that nitrogen incorporation induces significant structural rearrangements, manifested mainly by a change in boron coordination number from four to three, and by the formation of boron-nitrogen-boron bridges. The nature of boron-nitrogen bonding depends on the composition of the sputtering target, with an exponential relationship adequately describing the dependence of B-N stretching frequency on bond length. Besides bonding to two boron atoms by covalent bonds, the nitrogen atoms interact also with Li ions by participating in their coordination sphere together with oxygen atoms. Likely, boron-nitrogen bonding in LiBON films facilitates Li ion transport due to induced charge delocalization within the boron-nitrogen-boron bridges and reduced electrostatic interaction with the Li ions.
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| 32. |
- Eliasen, K. L., et al.
(författare)
-
High-frequency dynamics and test of the shoving model for the glass-forming ionic liquid Pyr14-TFSI
- 2021
-
Ingår i: Physical Review Materials. - 2475-9953. ; 5:6
-
Tidskriftsartikel (refereegranskat)abstract
- In studies of glass-forming liquids, one of the important questions is to understand to which degree chemically different classes of liquids have the same type of dynamics. In this context, room-temperature ionic liquids are interesting because they exhibit both van der Waals and Coulomb interactions. In this work we study the α relaxation and faster relaxation dynamics in the room-temperature ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14-TFSI). The paper presents quasielastic neutron and shear mechanical spectroscopy data measured over seven decades in frequency (10-3-104 Hz). The use of these two methods in combination reveal the α relaxation and four separate, faster modes. Two of these faster modes, based on the partial deuterations, can be assigned to the methyl group and the methyl end of the butyl chain of the cation. The neutron data are also used to determine the mean-square displacement (MSD) on the nanosecond timescale. It is shown that the temperature dependence of the MSD can account for the super-Arrhenius behavior of the α relaxation as predicted by the shoving model [Dyre, Rev. Mod. Phys. 78, 953 (2006)RMPHAT0034-686110.1103/RevModPhys.78.953], similarly to what is seen in simpler glass-forming liquids.
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| 33. |
- Flores, Eibar, 1990, et al.
(författare)
-
PRISMA: A Robust and Intuitive Tool for High-Throughput Processing of Chemical Spectra
- 2022
-
Ingår i: Chemistry-Methods. - : Wiley. - 2628-9725. ; 2:10
-
Tidskriftsartikel (refereegranskat)abstract
- Here we introduce PRISMA, an open-source tool to rapidly analyse large numbers of spectra into meaningful spectroscopic trends. PRISMA follows a human-in-the-loop workflow, where the user interacts with an intuitive graphical user interface to control multiple steps in the spectrum analysis process: trimming, baseline correction, and peak fitting. The tool outputs the results in an easy-to-read csv format within seconds. We describe the functionalities implemented in PRISMA and test its capabilities with three experimental cases relevant to the study of Electrochemical energy storage and conversion devices: a temperature-dependent Raman measurement of phase transitions, a linear Raman mapping of a graphite composite electrode, and an operando X-ray diffraction experiment of lithium nickel oxide composite battery electrode. The case studies demonstrate the robustness of the app and its ability to unearth insightful trends in peak parameters, which are easier to represent, interpret and further analyse with more advanced techniques.
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| 34. |
- Fretz, Samuel Joseph, 1987, et al.
(författare)
-
Amine- and Amide-Functionalized Mesoporous Carbons: A Strategy for Improving Sulfur/Host Interactions in Li-S Batteries
- 2020
-
Ingår i: Batteries and Supercaps. - : Wiley. - 2566-6223. ; 3:8, s. 757-765
-
Tidskriftsartikel (refereegranskat)abstract
- Lithium-sulfur (Li-S) batteries are of great interest due to their potentially high energy density, but the low electronic conductivity of both the sulfur (S-8) cathode active material and the final discharge product lithium sulfide (Li2S) require the use of a conductive host. Usually made of relatively hydrophobic carbon, such hosts are typically ill-suited to retain polar discharge products such as the intermediate lithium polysulfides (LiPs) and the final Li2S. Herein, we propose a route to increase the sulfur utilization by functionalizing the surface of ordered mesoporous carbon CMK3 with polar groups. These derivatized CMK3 materials are made using a simple two-step procedure of bromomethylation and subsequent nucleophilic substitution with amine or amide nucleophiles. We demonstrate that, compared to the unfunctionalized control, these modified CMK3 surfaces have considerably larger binding energies with LiPs and Li2S, which are proposed to aid the electrochemical conversion between S-8 and Li2S by keeping the LiPs species in close proximity to the carbon surface during Li-S battery cycling. As a result, the functionalized cathodes exhibit significantly improved specific capacities relative to their unmodified precursor.
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| 35. |
- Fu, Yifeng, 1984, et al.
(författare)
-
Selective growth of double-walled carbon nanotubes on gold films
- 2012
-
Ingår i: Materials Letters. - : Elsevier BV. - 1873-4979 .- 0167-577X. ; 72, s. 78-80
-
Tidskriftsartikel (refereegranskat)abstract
- Growth of high-quality vertical aligned carbon nanotube (CNT) structures on silicon supported gold (Au) films by thermal chemical vapor deposition (TCVD) is presented. Transmission electron microscopy (TEM) images show that the growth is highly selective. Statistical study reveals that 79.4% of the as-grown CNTs are double-walled. The CNTs synthesized on Au films are more porous than that synthesized on silicon substrates under the same conditions. Raman spectroscopy and electrical characterization performed on the as-grown double-walled CNTs (DWNTs) indicate that they are competitive with those CNTs grown on silicon substrates. Field emission tests show that closed-ended DWNTs have lower threshold field than those open-ended.
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| 36. |
- Fu, Yifeng, 1984, et al.
(författare)
-
Templated Growth of Covalently Bonded Three-Dimensional Carbon Nanotube Networks Originated from Graphene
- 2012
-
Ingår i: Advanced Materials. - : Wiley. - 0935-9648 .- 1521-4095. ; 24:12, s. 1576-1581
-
Tidskriftsartikel (refereegranskat)abstract
- A template-assisted method that enables the growth of covalently bonded three-dimensional carbon nanotubes (CNTs) originating from graphene at a large scale is demonstrated. Atomic force microscopy-based mechanical tests show that the covalently bonded CNT structure can effectively distribute external loading throughout the network to improve the mechanical strength of the material.
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| 37. |
- Ghai, Viney, 1989, et al.
(författare)
-
Achieving Long-Range Arbitrary Uniform Alignment of Nanostructures in Magnetic Fields
- 2024
-
Ingår i: Advanced Functional Materials. - 1616-3028 .- 1616-301X. ; In Press
-
Tidskriftsartikel (refereegranskat)abstract
- For magnetic field orientation of nonstructures to become a viable method to create high performance multifunctional nanocomposites, it is of paramount importance to develop a method that is easy to implement and that can induce long-range uniform nanostructural alignment. To overcome this challenge, inspired by low field nuclear magnetic resonance (NMR) technology, a highly uniform, high field strength, and compact magnetic-field nanostructure orientation methodology is presented for polymeric nanocomposites using a Halbach array, for the first time. Potential new advances are showcased for applications of graphene polymer composites by considering their electro-thermal and antibacterial properties in highly oriented orthogonal morphologies. The high level of anisotropy induced in the graphene nanocomposites studied stands out through: 1) up to four decades higher electrical conductivities recorded in comparison to their randomly oriented counterparts, at concentrations where the latter show minimal improvements compared to the unfilled polymer; 2) over 1200% improvement in thermal conductivity, 3) antibacterial surfaces at field benchmark levels with lower filler content and with the added versatility of arbitrary orientation of the nanofillers. Overall, the new method and variations thereof can open up new horizons for tailoring nanostructure and performance for virtually all major nanocomposite applications based on graphene and other types of fillers.
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| 38. |
- Ghanbari, Reza, 1984, et al.
(författare)
-
Painting Taylor vortices with cellulose nanocrystals: supercritical spectral dynamics
- 2023
-
Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- We study the flow stability and spatio-temporal spectral dynamics of cellulose nanocrystal (CNC) suspensions in a custom Taylor-Couette flow cell using the intrinsic shear induced birefringence and liquid crystalline properties of CNC suspensions for flow visualizations for the first time. The analysis is performed at constant ramped speed inputs of the independently rotating cylinders for several cases ranging from only inner or outer rotating cylinders to three counter-rotation cases. All CNC suspensions have measurable elastic and shear thinning, both increasing with CNC concentration. We show that the flow patterns recorded are essentially Newtonian-like, with non-Newtonian effects ranging from a decrease in wavenumbers to altering the critical parameters for the onset of instability modes. Outer cylinder rotation flow cases are stable for all concentrations whereas inner cylinder rotation flow cases transition to axisymmetric and azimuthally periodic secondary flows. However, unstable counter-rotation cases become unstable to asymmetric spiral modes. With increasing CNC concentration a counter-rotation case was found where azimuthally periodic wavy patterns transition to asymmetric spiral modes. In contrast to polymeric solutions of similar low to moderate elasticity and shear thinning, the shear-thinning region of CNC suspensions is expected to lead to the breakdown of the chiral nematic phase, whose elastic constants constitute the dominant structural elasticity mechanism. Thus, we interpret the Taylor-Couette stability of the CNC suspensions as dominated by their shear-thinning character due to the expected loss of elasticity in nonlinear flow conditions.
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| 39. |
- Ghanbari, Reza, 1984, et al.
(författare)
-
Painting Taylor vortices with cellulose nanocrystals: Suspension flow supercritical spectral dynamics
- 2024
-
Ingår i: Physics of Fluids. - 1089-7666 .- 1070-6631. ; 36:4
-
Tidskriftsartikel (refereegranskat)abstract
- We study the flow stability and spatiotemporal spectral dynamics of cellulose nanocrystal (CNC) suspensions in a custom Taylor-Couette flow cell using the intrinsic shear induced birefringence and liquid crystalline properties of CNC suspensions for flow visualizations, for the first time. The analysis is performed at constant ramped speed inputs of the independently rotating cylinders for several cases ranging from only inner or outer rotating cylinders to three counter-rotation cases. All CNC suspensions have measurable elasticity and shear thinning, both increasing with CNC concentration. We show that the flow patterns recorded are essentially Newtonian-like, with non-Newtonian effects ranging from a decrease in wavenumbers to altering the critical parameters for the onset of instability modes. Outer cylinder rotation flow cases are stable for all concentrations whereas inner cylinder rotation flow cases transition to axisymmetric and azimuthally periodic secondary flows. However, counter-rotation cases become unstable to asymmetric spiral modes. With increasing CNC concentration, a counter-rotation case was found where azimuthally periodic wavy patterns transition to asymmetric spiral modes. Based on rheo-SAXS measurements, the shear-thinning region of CNC suspensions is expected to lead to the breakdown of the chiral nematic phase, whose elastic constants constitute the dominant structural elasticity mechanism. Thus, we interpret the Taylor-Couette stability of the CNC suspensions as dominated by their shear-thinning character due to the expected loss of elasticity in nonlinear flow conditions.
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| 40. |
- Gkourmpis, Thomas, et al.
(författare)
-
Melt-Mixed 3D Hierarchical Graphene/Polypropylene Nanocomposites with Low Electrical Percolation Threshold
- 2019
-
Ingår i: Nanomaterials. - : MDPI AG. - 2079-4991. ; 9:12
-
Tidskriftsartikel (refereegranskat)abstract
- Graphene-based materials are a family of carbonaceous structures that can be produced using a variety of processes either from graphite or other precursors. These materials are typically a few layered sheets of graphene in the form of platelets and maintain some of the properties of pristine graphene (such as two-dimensional platelet shape, aspect ratio, and graphitic bonding). In this work we present melt mixed graphene-based polypropylene systems with significantly reduced percolation threshold. Traditionally melt-mixed systems suffer from poor dispersion that leads to high electrical percolation values. In contrast in our work, graphene was added into an isotactic polypropylene matrix, achieving an electrical percolation threshold of similar to 1 wt.%. This indicates that the filler dispersion process has been highly efficient, something that leads to the suppression of the beta phase that have a strong influence on the crystallization behavior and subsequent thermal and mechanical performance. The electrical percolation values obtained are comparable with reported solution mixed systems, despite the use of simple melt mixing protocols and the lack of any pre or post-treatment of the final compositions. The latter is of particular importance as the preparation method used in this work is industrially relevant and is readily scalable.
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| 41. |
- Hansen, Henriette Wase, 1988, et al.
(författare)
-
Density scaling of structure and dynamics of an ionic liquid
- 2020
-
Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9084 .- 1463-9076. ; 22:25, s. 14169-14176
-
Tidskriftsartikel (refereegranskat)abstract
- Room temperature ionic liquids are salts with low melting points achieved by employing bulky and asymmetrical ions. The molecular design leads to apolar and polar parts as well as the presence of competing Coulomb and van der Waals interactions giving rise to nano-scale structure, e.g. charge ordering. In this paper we address the question of how these nano-scale structures influence transport properties and dynamics on different timescales. We apply pressure and temperature as control parameters and investigate the structure factor, charge transport, microscopic alpha relaxation and phonon dynamics in the phase diagram of an ionic liquid. Including viscosity and self diffusion data from literature we find that all the dynamic and transport variables studied follow the same density scaling, i.e. they all depend on the scaling variable Γ = ργ/T, with γ = 2.8. The molecular nearest neighbor structure is found to follow a density scaling identical to that of the dynamics, while this is not the case for the charge ordering, indicating that the charge ordering has little influence on the investigated dynamics.
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| 42. |
- Haridas, Anupriya K., et al.
(författare)
-
A flexible and free-standing FeS/sulfurized polyacrylonitrile hybrid anode material for high-rate sodium-ion storage
- 2020
-
Ingår i: Chemical Engineering Journal. - : Elsevier BV. - 1385-8947. ; 385:1 April
-
Tidskriftsartikel (refereegranskat)abstract
- Sodium-ion based energy storage systems have attracted extensive attention due to the similarities in the mechanism of operation with lithium-ion batteries along with the additional benefit of low cost and high abundance of sodium resources. Iron sulfide-based electrodes that operate via conversion mechanism have shown ample potential for high energy sodium-ion storage. However, the problems related with tremendous volume changes and the dissolution of sodium polysulfides in the electrolyte deteriorate the cycle life and limit their application in sodium-ion batteries (SIBs). Herein, a hybrid anode material, FeS/SPAN-HNF, with iron sulfide (FeS) nanoparticles decorated in a sulfurized polyacrylonitrile (SPAN) fiber matrix is demonstrated as flexible and free-standing anode material for high-rate SIBs. Unlike previous strategies in which FeS is encapsulated in an electrochemically inactive carbon matrix, this study utilizes SPAN, an electrochemically active material, as a dual functional matrix that can efficiently buffer volume expansion and sulfur dissolution of FeS nanoparticles as well as provide significant capacity improvement. The as-designed electrode is self-standing and flexible, without current collectors, binders or additional conductive agents, thus rendering enhanced practical capacity and energy density. This electrode showed a high reversible capacity of 782.8 mAh g−1 at 200 mA g−1 with excellent high rate capability, maintaining 327.5 mAh g−1 after 500 cycles at 5 A g−1, emphasizing promising prospects for the development of flexible and high energy density SIBs.
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| 43. |
- Haridas, Anupriya K., et al.
(författare)
-
An Electrospun Core–Shell Nanofiber Web as a High-Performance Cathode for Iron Disulfide-Based Rechargeable Lithium Batteries
- 2018
-
Ingår i: ChemSusChem. - : Wiley. - 1864-5631 .- 1864-564X. ; 11:20, s. 3625-3630
-
Tidskriftsartikel (refereegranskat)abstract
- FeS2/C core–shell nanofiber webs were synthesized for the first time by a unique synthesis strategy that couples electrospinning and carbon coating of the nanofibers with sucrose. The design of the one-dimensional core–shell morphology was found to be greatly beneficial for accommodating the volume changes encountered during cycling, to induce shorter lithium ion diffusion pathways in the electrode, and to prevent sulfur dissolution during cycling. A high discharge capacity of 545 mAh g−1 was retained after 500 cycles at 1 C, exhibiting excellent stable cycling performance with 98.8 % capacity retention at the last cycle. High specific capacities of 854 mAh g−1, 518 mAh g−1, and 208 mAh g−1 were obtained at 0.1 C, 1 C, and 10 C rates, respectively, demonstrating the exceptional rate capability of this nanofiber web cathode.
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| 44. |
- Haridas, Anupriya K., et al.
(författare)
-
Boosting High Energy Density Lithium-Ion Storage via the Rational Design of an FeS-Incorporated Sulfurized Polyacrylonitrile Fiber Hybrid Cathode
- 2019
-
Ingår i: ACS Applied Materials & Interfaces. - : American Chemical Society (ACS). - 1944-8252 .- 1944-8244. ; 11:33, s. 29924-29933
-
Tidskriftsartikel (refereegranskat)abstract
- In order to satisfy the escalating energy demands, it is inevitable to improve the energy density of current Li-ion batteries. As the development of high-capacity cathode materials is of paramount significance compared to anode materials, here we have designed for the first time a unique synergistic hybrid cathode material with enhanced specific capacity, incorporating cost-effective iron sulfide (FeS) nanoparticles in a sulfurized polyacrylonitrile (SPAN) nanofiber matrix through a rational in situ synthesis strategy. Previous reports on FeS cathodes are scarce and consist of an amorphous carbon matrix to accommodate the volume changes encountered during the cycling process. However, this inactive buffering matrix eventually increases the weight of the cell, reducing the overall energy density. By the rational design of this hybrid composite cathode, we ensure that the presence of covalently bonded sulfur in SPAN guarantees high sulfur utilization, while effectively buffering the volume changes in FeS. Meanwhile, FeS can compensate for the conductivity issues in the SPAN, thereby realizing a synergistically driven dual-active cathode material improving the overall energy density of the composite. Simultaneous in situ generation of FeS nanoparticles within the SPAN fiber matrix was carried out via electrospinning followed by a one-step heating procedure. The developed hybrid cathode material displays enhanced lithium-ion storage, retaining 688.6 mA h g(FeS@SPAN composite)-1 at the end of 500 cycles at 1 A g-1 even within a narrow voltage range of 1-3.0 V. A high discharge energy density > 900 W h kg(FeS@SPAN composite)-1, much higher than the theoretical energy density of the commercial LiCoO2 cathode, was also achieved, revealing the promising prospects of this hybrid cathode material for high energy density applications.
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| 45. |
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| 46. |
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| 47. |
- Iselau, Frida, 1979, et al.
(författare)
-
Competitive adsorption of amylopectin and amylose on cationic nanoparticles: a study on the aggregation mechanism
- 2016
-
Ingår i: Soft Matter. - : Royal Society of Chemistry (RSC). - 1744-6848 .- 1744-683X. ; 12:14, s. 3388-3397
-
Tidskriftsartikel (refereegranskat)abstract
- In this study we investigate the interactions between cationic nanoparticles and anionic starch, where the starch was composed of 20 wt% of amylose, a linear polymer, and 80 wt% of amylopectin, a branched polymer. The mechanism of aggregation was investigated by scattering techniques. It was found that the cationic particles formed large aggregates with the starch as a result of selective adsorption of the amylopectin. Amylose did not participate significantly in the aggregate formation even when the charge ratio of starch to particles was <1. For starch to particle ratio 41 stabilization was recovered mostly due to the large hindrance brought about by the highly branched amylopectin. This results in a shift of the stabilization mechanism from electrostatic to electrosteric. The internal structure of the aggregates was composed of primary particles with starch coils adsorbed on the surface. This information supports the proposed aggregation mechanism, which is based on adsorption of the negatively charged starch in patches on the positively charged nanoparticles causing attractive interaction between the particles.
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| 48. |
- Iselau, Frida, 1979, et al.
(författare)
-
Formation and relaxation kinetics of starch-particle complexes
- 2016
-
Ingår i: Soft Matter. - 1744-6848 .- 1744-683X. ; 12:47, s. 9509-9519
-
Tidskriftsartikel (refereegranskat)abstract
- The formation and relaxation kinetics of starch-particle complexes were investigated in this study. The combination of cationic nanoparticles in suspension and anionic starch in solution gave rise to aggregate formation which was studied by dynamic light scattering, revealing the initial adsorption of the starch molecules on the particle surface. By examining the stability ratio, W, it was found that even in the most destabilized state, i.e. at charge neutralization, the starch chains had induced steric stabilization to the system. At higher particle and starch concentrations relaxation of the aggregates could be seen, as monitored by a decrease in turbidity with time. This relaxation was evaluated by fitting the data to the Kohlrausch-Williams-Watts function. It was found that irrespective of the starch to particle charge ratio the relaxation time was similar. Moreover, a molecular weight dependence on the relaxation time was found, as well as a more pronounced initial aggregated state for the higher molecular weight starch. This initial aggregate state could be due to bridging flocculation. With time, as the starch chains have relaxed into a final conformation on the particle surface, bridging will be less important and is gradually replaced by patches that will cause patchwise flocculation. After an equilibration time no molecular weight dependence on aggregation could be seen, which confirms the patchwise flocculation mechanism.
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| 49. |
- Izzo, M. G., et al.
(författare)
-
Rayleigh scattering and disorder-induced mixing of polarizations in amorphous solids at the nanoscale: 1-octyl-3-methylimidazolium chloride glass
- 2020
-
Ingår i: Physical Review B. - 2469-9969 .- 2469-9950. ; 102:21
-
Tidskriftsartikel (refereegranskat)abstract
- Acousticlike excitations in topologically disordered media at mesocale/nanoscale present anomalous features with respect to the Debye's theory. The so-called Rayleigh scattering manifests in a strong increase of the attenuation of the acousticlike excitations and a softening of the phase velocity with respect to its continuum limit value. Mean field models developed in the random media theory framework can successfully predict the occurrence, at the proper length scale, of Rayleigh scattering. The overall attenuation in the Rayleigh region is, however, underestimated. In the framework of random media theory we developed an analytical model, which permits a quantitative description of the acousticlike excitations in topological glasses in the whole first pseudo-Brillouin zone. The underestimation of the Rayleigh scattering is avoided and, importantly, the model allows to account also for the polarization properties of the acousticlike excitations. In a three-dimensional medium an acoustic wave is characterized by its phase velocity, intensity, and polarization. Rayleigh scattering emphasizes how the topological disorder affects the first two properties. The topological disorder is, however, expected to influence also the third one. In common with the Rayleigh scattering, hallmarks possibly related to the mixing of polarizations have been traced in different classes of amorphous solids at nanoscale. The quantitative theoretical approach developed permits to demonstrate how the mixing of polarizations generates a distinctive feature in the dynamic structure factor of amorphous solids. The modeling capability of the proposed mean field theory is tested on glassy 1-octyl-3-methylimidazolium chloride, whose spatial distribution of the elastic moduli is well assessed and can be experimentally characterized. Contrast between theoretical and experimental features for the selected glass reveals an excellent agreement. The mean field approach we present retains a certain degree of generality and can be possibly extended to different stochastic media or different wave fields.
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| 50. |
- Jacquet, Quentin, et al.
(författare)
-
A Fundamental Correlative Spectroscopic Study on Li 1-x NiO 2 and NaNiO 2
- 2024
-
Ingår i: Advanced Energy Materials. - 1614-6840 .- 1614-6832. ; In Press
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Tidskriftsartikel (refereegranskat)abstract
- The intricate relationship between local atomic arrangements and electronic states significantly influences the electrochemical properties of Li-ion battery cathode materials. Despite decades of investigation, a consensus regarding the local atomic and electronic structure of LiNiO2 remains elusive. This ambiguity stems from the potential distortion of Ni sites, either via Jahn-Teller (JT) distortion or bond disproportionation (BD), complicating the understanding of the charge compensation mechanism involving Ni and O. This study compares the structures of LiNiO2 and NaNiO2, a JT system, using an innovative approach that integrates bulk spectroscopy techniques on standardized interoperable samples for enhanced reliability. While X-r and theoretical calculations fail to differentiate between the proposed scenarios, Raman spectroscopy highlights local structural distinctions between monoclinic NaNiO2 and rhombohedral LiNiO2. HAXPES confirms various formal oxidation states for Ni, supported by RIXS data indicating 3d8 states, emphasizing negative charge transfer from Ni and some bond disproportionation in LiNiO2. Regarding charge compensation, XRS and RIXS suggest oxygen hole involvement in redox activity, whereas Raman spectroscopy does not detect molecular oxygen. This comprehensive spectroscopic analysis highlights the importance of correlative characterization workflows in elucidating complex structural-electrochemical relationships.
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