| 11. |
- Araujo, Rafael B., et al.
(author)
-
Designing strategies to tune reduction potential of organic molecules for sustainable high capacity batteries application
- 2017
-
In: Journal of Materials Chemistry A. - 2050-7488 .- 2050-7496. ; 5:9, s. 4430-4454
-
Journal article (peer-reviewed)abstract
- Organic compounds evolve as a promising alternative to the currently used inorganic materials in rechargeable batteries due to their low-cost, environmentally friendliness and flexibility. One of the strategies to reach acceptable energy densities and to deal with the high solubility of known organic compounds is to combine small redox active molecules, acting as capacity carrying centres, with conducting polymers. Following this strategy, it is important to achieve redox matching between the chosen molecule and the polymer backbone. Here, a synergetic approach combining theory and experiment has been employed to investigate this strategy. The framework of density functional theory connected with the reaction field method has been applied to predict the formal potential of 137 molecules and identify promising candidates for the referent application. The effects of including different ring types, e.g. fused rings or bonded rings, heteroatoms, [small pi] bonds, as well as carboxyl groups on the formal potential, has been rationalized. Finally, we have identified a number of molecules with acceptable theoretical capacities that show redox matching with thiophene-based conducting polymers which, hence, are suggested as pendent groups for the development of conducting redox polymer based electrode materials.
|
|
| 12. |
- Araujo, Rafael B., et al.
(author)
-
Designing strategies to tune reduction potential of organic molecules for sustainable high capacity battery application
- 2017
-
In: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 5:9, s. 4430-4454
-
Journal article (peer-reviewed)abstract
- Organic compounds evolve as a promising alternative to currently used inorganic materials in rechargeable batteries due to their low-cost, environmental friendliness and flexibility. One of the strategies to reach acceptable energy densities and to deal with the high solubility of known organic compounds is to combine small redox active molecules, acting as capacity carrying centres, with conducting polymers. Following this strategy, it is important to achieve redox matching between the chosen molecule and the polymer backbone. Here, a synergetic approach combining theory and experiment has been employed to investigate this strategy. The framework of the density functional theory connected with the reaction field method has been applied to predict the formal potential of 137 molecules and identify promising candidates for the referent application. The effects of including different ring types, e.g. fused rings or bonded rings, heteroatoms, and pi bonds, as well as carboxyl groups on the formal potential, have been rationalized. Finally, we have identified a number of molecules with acceptable theoretical capacities that show redox matching with thiophene-based conducting polymers which, hence, are suggested as pendent groups for the development of conducting redox polymer based electrode materials.
|
|
| 13. |
- Araujo, Rafael B., et al.
(author)
-
Predicting electrochemical properties and ionic diffusion in Na2+2xMn2-x(SO4)(3) : crafting a promising high voltage cathode material
- 2016
-
In: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 4:2, s. 451-457
-
Journal article (peer-reviewed)abstract
- Sodium ion batteries have emerged as a good alternative to lithium based systems due to their low cost of production. In this scenario, the search for higher voltage, sodium cathodes results in a new promising alluaudite structure Na2+2xMn2-x(SO4)(3). The structural, electronic and Na diffusion properties along with defects have been reported in this investigation within the framework of density functional theory. A band gap of 3.61 eV has been computed and the average deintercalation potential is determined to be 4.11 V vs. Na/Na+. A low concentration of anti-site defects is predicted due to their high formation energy. The biggest issue for the ionic diffusion in the Na2+2xMn2-x(SO4)(3) crystal structure is revealed to be the effect of Mn vacancies increasing the activation energy of Na+ ions that hop along the [001] equilibrium positions. This effect leads to activation energies of almost the same high values for the ionic hop through the [010] direction characterizing a 2D like ionic diffusion mechanism in this system.
|
|
| 14. |
- Araujo, Rafael, et al.
(author)
-
N-2 adsorption on high-entropy alloy surfaces : unveiling the role of local environments
- 2023
-
In: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 11:24, s. 12973-12983
-
Journal article (peer-reviewed)abstract
- Developing highly active catalysts to electrochemically reduce N-2 to NH3 under ambient conditions is challenging but bears the promise of using ammonia as a potential energy vector in sustainable energy technology. One of the scientific challenges concerns the inertness of N-2 emanating from the highly stable triple bonds and the lack of dipole moments, making N-2 fixation on catalytic surfaces difficult. Another critical challenge is that electrons are more prone to reduce hydrogen than N-2 at the surface, forming a scaling relationship where the reduction ability of the catalyst most often benefits hydrogen reduction instead of nitrogen reduction. Here we show that high-entropy alloys (HEA) - a new class of catalysts with vast compositional and structural possibilities, can enhance N-2 fixation. More specifically, we investigate the role of the local environment in the first and second solvation shell of the adsorbing elements in the bond strength between the dinitrogen molecules and the HEA surfaces. Density functional theory using a Bayesian error estimation functional and vdW interactions is employed to clarify the properties dictating the local bonding. The results show that although the main property calibrating the N-2 bond strength is the d-band centers of the adsorbing elements, the value of the d-band centers of the adsorbing elements is further regulated by their local environment, mainly from the elements in the first solvation shell due to electron donor-acceptor interactions. Therefore, there exists a first solvation shell effect of the adsorbing elements on the bond strength between N-2 molecules and the surface of HEAs. The results show that apart from the direct active site, the indirect relation adds further modulation abilities where the local interactions with a breath of metallic elements could be used in HEAs to engineer specific surface environments. This is utilized here to form a strategy for delivering higher bond strength with the N-2 molecules, mitigating the fixation issue. The analysis is corroborated by correlation analysis of the properties affecting the interaction, thus forming a solid framework of the model, easily extendable to other chemical reactions and surface interaction problems.
|
|
| 15. |
- Arvizu, Miguel A, et al.
(author)
-
Electrochromic WO3 thin films attain unprecedented durability by potentiostatic pretreatment
- 2019
-
In: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 7:6, s. 2908-2918
-
Journal article (peer-reviewed)abstract
- Electrochromic windows and glass facades are able to impart energy efficiency jointly with indoor comfort and convenience. Long-term durability is essential for practical implementation of this technology and has recently attracted broad interest. Here we show that a simple potentiostatic pretreatment of sputterdeposited thin films of amorphous WO3-the most widely studied electrochromic material-can yield unprecedented durability for charge exchange and optical modulation under harsh electrochemical cycling in a Li-ion-conducting electrolyte and effectively evades harmful trapping of Li. The pretreatment consisted of applying a voltage of 6.0 V vs. Li/Li+ for several hours to a film backed by a transparent conducting In2O3: Sn layer. Associated compositional and structural modifications were probed by several techniques, and improved durability was associated with elemental intermixing at the WO3/ITO and ITO/glass boundaries as well as with carbonaceous solid-electrolyte interfacial layers on the WO3 films. Our work provides important new insights into long-term durability of ion-exchange-based devices.
|
|
| 16. |
- Banerjee, Amitava, et al.
(author)
-
Bromination-induced stability enhancement with a multivalley optical response signature in guanidinium [C(NH2)(3)](+)-based hybrid perovskite solar cells
- 2017
-
In: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 5:35, s. 18561-18568
-
Journal article (peer-reviewed)abstract
- Guanidinium lead iodide (GAPbI(3)) has been synthesized experimentally, but stability remains an issue, which can be modulated by the insertion of bromine (Br) into the system. We have performed a systematic theoretical investigation to see how bromination can tune the stability of GAPbI(3). The optical properties were also determined, and we have found formation enthalpy-based stability in the perovskite systems, which are active in the visible and IR region even after bromine insertion and additionally more active in the IR range with the transition from GAPbI(3) to GAPbBr(3). The spin orbit coupling effect is considered throughout the band structure calculations. The ensemble of the primary and secondary gaps in the half and fully brominated hybrid perovskites leads to the phenomenon of a multipeak response in the optical spectra, which can be subsequently attributed as multivalley optical response behaviour. This multivalley optical behaviour enables the brominated guanidinium-based hybrid perovskites to exhibit broad light harvesting abilities, and this can be perceived as an idea for natural multi-junction solar cells.
|
|
| 17. |
- Banerjee, Amitava, et al.
(author)
-
Promise and reality of organic electrodes from materials design and charge storage perspective
- 2022
-
In: Journal of Materials Chemistry A. - : Royal Society of Chemistry (RSC). - 2050-7488 .- 2050-7496. ; 10:29, s. 15215-15234
-
Research review (peer-reviewed)abstract
- Organic electrode materials are becoming increasingly important as they reduce the C-footprint as well as the production cost of currently used and studied rechargeable batteries. With increasing demand for high-energy-density devices, over the past few decades, various innovative new materials based on the fundamental structure-property relationships and molecular design have been explored to enable high-capacity next-generation battery chemistries. One critical dimension that catalyzes this study is the building up of an in-depth understanding of the structure-property relationship and mechanism of alkali ion batteries. In this review, we present a critical overview of the progress in the technical feasibility of organic battery electrodes for use in long-term and large-scale electrical energy-storage devices based on the materials designing, working mechanisms, performance, and battery safety. Specifically, we discuss the underlying alkali ion storage mechanisms in specific organic batteries, which could provide the designing requirements to overcome the limitations of organic batteries. We also discuss the promising future research directions in the field of alkali ion organic batteries, especially multivalent organic batteries along with monovalent alkali ion organic batteries.
|
|
| 18. |
- Banerjee, Amitava, et al.
(author)
-
Unveiling the thermodynamic and kinetic properties of NaxFe(SO4)(2) (x=0-2) : toward a high-capacity and low-cost cathode material
- 2016
-
In: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488 .- 2050-7496. ; 4:46, s. 17960-17969
-
Journal article (peer-reviewed)abstract
- The mineral eldfellite, NaFe(SO4)(2), was recently proposed as an inexpensive candidate for the next generation of cathode application in Na-based batteries. Employing the density functional theory framework, we have investigated the phase stability, electrochemical properties and ionic diffusion of this eldfellite cathode material. We showed that the crystal structure undergoes a volume shrinkage of approximate to 8% upon full removal of Na ions with no imaginary frequencies at the Gamma point of phonon dispersion. This evokes the stability of the host structure. According to this result, we proposed structural changes to get higher specific energy by inserting two Na ions per redox-active metal. Our calculations indicate NaV(SO4)(2) as the best candidate with the capability of reversibly inserting two Na ions per redox center and producing an excellent specific energy. The main bottleneck for the application of eldfellite as a cathode is the high activation energies for the Na+ ion hop, which can reach values even higher than 1 eV for the charged state. This effect produces a low ionic insertion rate.
|
|
| 19. |
- Bao, Qinye, et al.
(author)
-
Effects of ultraviolet soaking on surface electronic structures of solution processed ZnO nanoparticle films in polymer solar cells
- 2014
-
In: Journal of Materials Chemistry A. - : Royal Society of Chemistry. - 2050-7488. ; 2:41, s. 17676-17682
-
Journal article (peer-reviewed)abstract
- We systematically show the effect of UV-light soaking on surface electronic structures and chemical states of solution processed ZnO nanoparticle (ZnONP) films in UHV, dry air and UV-ozone. UV exposure in UHV induces a slight decrease in work function and surface-desorption of chemisorbed oxygen, whereas UV exposure in the presence of oxygen causes an increase in work function due to oxygen atom vacancy filling in the ZnO matrix. We demonstrate that UV-light soaking in combination with vacuum or oxygen can tune the work function of the ZnONP films over a range exceeding 1 eV. Based on photovoltaic performance and diode measurements, we conclude that the oxygen atom vacancy filling occurs mainly at the surface of the ZnONP films and that the films consequently retain their n-type behavior despite a significant increase in the measured work function.
|
|
| 20. |
- Barzgar Vishlaghi, Mahsa, et al.
(author)
-
Accelerating water oxidation on BiVO 4 photoanodes via surface modification with Co dopants
- 2023
-
In: Journal of Materials Chemistry A. - 2050-7488 .- 2050-7496. ; 11:31, s. 16648-16658
-
Journal article (peer-reviewed)abstract
- Despite the vast investigations on improving the photoelectrochemical performance of BiVO4 for water splitting, charge recombination in the near-surface region remains a challenge. In this study, we showed that the diffusion of Co2+ ions into the BiVO4 subsurface boosted the water oxidation activity and charge injection efficiency remarkably. The increase in the concentration of oxygen vacancies upon the incorporation of cobalt ions was shown by electron paramagnetic resonance (EPR) spectroscopy and confirmed by density functional theory (DFT) calculations. DFT calculations revealed that vanadium sites in the subsurface region were the most favorable sites for substitution with cobalt ions. Charge localization at surface oxygen vacancies was found less favorable in the presence of cobalt in the subsurface layer, eliminating surface recombination. This resulted in 4.25 times larger charge injection efficiency and 6.2 times higher photocurrent density at the potential of ∼0.6 V, as compared to pristine BiVO4. This enhancement was significantly larger as compared to CoOx-loaded BiVO4, indicating that the suppressed recombination at the surface and improved charge transfer kinetics obtained solely by CoOx deposition are not sufficient for enhanced activity of BiVO4. A longer charge carrier lifetime obtained upon cobalt incorporation was observed by transient absorption spectroscopy and verified the reduced rate of recombination.
|
|
