bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) Silicon Nanocrystals and Electrum Nanoclusters with High Quantum Yield for Light Converting Applications
Authors: Sychugov Ilya 
Published: August 2024

While QDs are typically made of semiconductors, metals at low dimensions also turn to discrete electronic structure. The characteristic transition size from bulk to nanodot is lower, because Fermi level position is at the band middle, while discretization of levels starts from the band edge. Therefore, only for sizes of a metal entity ~ 1 nm a QD-like behavior manifests.
Here we show that metal nanoclusters Au16Ag7 of an electrum alloy (gold-silver) with adamantanethiolate ligands possess PL quantum yield of ~ 70% in a thiol-ene polymer matrix [1]. PL is in NIR range with a large Stokes shift. Due to parity-forbidden transition the PL lifetime is in microseconds. These characteristics are similar to silicon QDs, where optical transition is also partly forbidden. Luminescence from Si QDs (5-10 nm size) may also feature high quantum efficiency when a defect-free core with good surface passivation is prepared. We have demonstrated a new synthesis method, which can reduce precursor cost by an order of magnitude from the established HSQ-based technique [2]. Si QDs prepared in this way have near-unity internal and > 50% external (quantum yield) efficiency with a large Stokes shift. In both nanomaterials the re-absorption is suppressed, which is of value for several applications.
One such application is a semi-transparent photovoltaics for glazing in building-integration. It is based on a luminescent solar concentrator concept, where high efficiency and a large Stokes shift are necessary requirements for nanophosphors. In this configuration absorbed solar light is re-emitted and a large fraction of it is guided by total internal reflection to the edges for collection by standard solar cells. As a proof-of-concept we fabricated 20x20 cm2 prototypes, where Si QD-doped polymer layer is sandwiched between glass plates in a triplex geometry. Such “solar windows” feature high transparency (>80%), low haze (<3%), high color rendering index (~ 88) and, at the same time, deliver up to 0.6 W of electrical peak power under one sun [3]. Original measurement techniques were developed to characterize large-area devices [4,5].

References

[1] M. Jash, X. Lu, J. Zhou, and I. Sychugov, "Electrum Nanoclusters in Polymer Composites with Quantum Yield Exceeding 70%" submitted (2024).
[2]J. Zhou, J. Huang, H. Chen, A. Samanta, J. Linnros, Z. Yang, and I. Sychugov, "Low-Cost Synthesis of Silicon Quantum Dots with Near-unity Internal Quantum Efficiency" J. Phys. Chem. Lett. 12, 8909−8916 (2021).
[3] J. Huang, J. Zhou, E. Jungstedt, A. Samanta, J. Linnros, L. Berglund, and I. Sychugov, "Large-area Transparent “Quantum Dots Glass” for Building Integrated Photovoltaics" ACS Photonics 9, 2499 (2022).
[4] J. Zhou, J. Huang, and l. Sychugov, "Optical Center of a Luminescent Solar Concentrator" Opt. Lett. 47, 4985 (2022).
[5] X. Lu, J. Zhou, M. Jash, and I. Sychugov, "Luminescence Solar Concentrator Efficiency versus Edge Solar Cell Coverage" Opt. Lett. 48, 4197 (2023).
(Invited) Electrochemistry of CdSe Quantum Dots in Organic Solvents. from Stochastic Electrochemistry to Film Behavior
Authors: Alpuche-Aviles Mario A. , Corona-Elizarraras Luis 
Published: August 2024

We present our electrochemistry results of CdSe quantum dots in two organic solvents: neat methanol and acetonitrile. In MeOH, the quantum dots (QDs) can be detected through stochastic collisions; that is, as agglomerates of QDs collide with an electrode surface, the photocurrent changes as a result of the CdSe entities that collide with the electrode surface.1 The experiment presented here uses Pt ultramicroelectrodes (UME), that is, electrodes with a diameter of 25 μm or less. Our results show that the CdSe can accumulate on the surface of the electrode, and the technique provides a high degree of control. By controlling the time the electrode collects QDs, one can control the amount of CdSe that accumulates at the electrode surface. After collecting CdSe on the surface, we perform cyclic voltammetry experiments to confirm that the electrode surface has changed. In acetonitrile (MeCN), we can perform CVs over large potential windows to study the electrochemistry of the deposited CdSe. The electrochemical response of the deposited CdSe resembles that of a film, although the surface has sub-monolayer coverages, as will be discussed from the images of scanning electron microscopy (SEM).
Figure 1 shows an example of a LSV in a region of interest where the current due to the CdSe significantly deviates from the background current. The LSV was run in the dark, so the current in the figure is a function of the density of states in the CdSe structures. It is also a function of the reversibility of the CV, i.e., mainly of the scan rate of the experiment. After the CV experiments, the Pt UME can be imaged in the SEM to correlate the electrochemical results with the CdSe deposited on the electrode surface. We will discuss our findings in terms of the results in the literature on CdSe electrochemistry (e.g., refs 2-5).

References.

(1) Subedi, P.; Parajuli, S.; Alpuche-Aviles, M. A., "Single Entity Behavior of CdSe Quantum Dot Aggregates During Photoelectrochemical Detection", Frontiers in Chemistry
9 (2021) DOI: 10.3389/fchem.2021.733642
(2) Kohl, P. A.; Bard, A. J., "Semiconductor electrodes. 13. Characterization and behavior of n-type zinc oxide, cadmium sulfide, and gallium phosphide electrodes in acetonitrile solutions", Journal of the American Chemical Society
99, 7531-7539 (1977) DOI: 10.1021/ja00465a023
(3) Hines, M. A.; Guyot-Sionnest, P., "Synthesis and characterization of strongly luminescing ZnS-capped CdSe nanocrystals", The Journal of Physical Chemistry
100, 468-471 (1996) DOI: 10.1021/jp9530562
(4) Zhang, J. Z., "Interfacial Charge Carrier Dynamics of Colloidal Semiconductor Nanoparticles", The Journal of Physical Chemistry B
104, 7239-7253 (2000) DOI: 10.1021/jp000594s
(5) Myung, N.; Ding, Z.; Bard, A. J., "Electrogenerated chemiluminescence of CdSe nanocrystals", Nano Letters
2, 1315-1319 (2002)

Figure 1
Stability in Photoluminescence and Photovoltaic Properties of Formamidinium Lead Iodide Quantum Dots
Authors: Svrcek Vladimir , Alessi Bruno , McDonald Calum , Mariotti Davide , Matsui Takuya 
Published: August 2024

Formamidinium lead iodide (FAPI) thin films in the perovskite crystalline phase have piqued interest for single-junction solar cells due to their optimal bandgap, long photocarrier lifetime, and intrinsic structural stability. However, trap states on the surface and within the lattice impede the performance and stability of FAPI bulk crystalline film cells. Strategies such as film crystallization, deposition optimization, precursor engineering, and interface property tailoring aim to overcome these limitations. One approach involves forming FAPI quantum dots (QDs). By reducing the size, we achieve better quality and stable alpha-phase FAPI on a nanometer scale. In this contribution, we report synthesizing of alpha-phase FAPI QDs with a mean size distribution of 20 nm. These QDs exhibit a narrow photoluminescence emission peak at 1.61 eV and higher absolute quantum yields ranging from 70% to 86%. Compared to bulk FAPI with a 1.54 eV gap, a blue shift is observed due to the quantum confinement effect.
However, achieving degradation-free perovskite solar cells under prolonged light soaking remains a challenge. Furthermore, we investigate the stability of FAPI bulk and QDS films in a humid chamber and after exposure to AM1.5G light in a humid setting (RH ~ 30%, T ~ 28°C). Our approach allows us to form homogeneously dispersed films of quantum dots with thicknesses of several hundred nanometers. These films are studied for photoluminescence and photovoltaic properties. Prototype solar cells incorporating synthesized FAPI QDs showed a power conversion efficiency of around 8%. These findings indicate considerably more stability in photoluminescence and photovoltaic properties of FAPI QDs for enhanced light-soaking stability compared to bulk FAPI films.
Designing Better Li Metal Anodes for Next-Generation Batteries
Authors: Wood Marissa , Xiao Yiran , Freyman Megan C. , Wang Bo , Zhu Cheng , Li Sichi 
Published: August 2024

Li metal batteries have the potential to significantly advance battery technology due to their substantially higher energy densities. However, robust high-capacity Li metal anodes are necessary to realize this approach, and current Li metal anode designs suffer from significant degradation over time due to non-uniform Li plating/stripping during cycling, which can lead to dead Li and/or Li dendrite growth. Carbon scaffold hosts can help mitigate this problem by creating a uniform electric field and providing abundant Li nucleation sites, but the relationship between the host architecture and performance is not well understood. We investigated the effect of scaffold architecture and chemistry on the resulting Li morphology and electrochemical performance using a combined experiment/theory approach. Carbon scaffolds with well-controlled geometries and varied porosities were fabricated using 3D printing and then characterized by SEM, Raman, and XPS before cycling in cells to evaluate their performance as hosts for uniform Li plating/stripping with both liquid and solid electrolytes. Atomistic and mesoscale modeling were used to predict how scaffold chemistry and microstructure affect Li nucleation probability and the formation of current density/stress hotspots that can lead to dendrite growth, and these results were used to help guide scaffold design. This work provides further insight into the relationship between anode architecture and Li metal cycling stability, which will facilitate the development of high-energy-density batteries in the future.
Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the U.S. Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344.
(Invited) Plasma Reforming of Liquid Hydrocarbons
Authors: Lim Norleakvisoth , Gordon Michael J. 
Published: August 2024

Engineering systems that more sustainably use our natural resources is central to both reducing the risks associated with CO2 emissions and making the long-term transition to a more circular, sustainable, and electrified economy. In particular, developing electrically driven technologies to leverage the energy density of liquids to produce clean fuels, e.g., H2, without making CO2, could be game changing. Here, we investigate the potential of directly exciting plasmas in liquid hydrocarbons to create multi-phase reaction environments, i.e., environments where plasma (ionized gas), H2, gaseous and liquid hydrocarbons, and solid carbon are all present simultaneously, to produce H2, unsaturated C2s, and carbon. The ultimate target is direct transformation of liquid hydrocarbons to gaseous H2 and solid, easy-to-separate carbon using electricity that can be provided from any source and/or points of use.
This talk will focus on our recent experiments to strike and sustain low and high frequency plasma discharges in liquid hydrocarbon jets to simultaneously generate gaseous H2, C2s, and solid carbon at high rates. Preliminary experiments show that (i) input energy is not wasted in simply vaporizing the liquid - so the system’s specific energy input preferentially drives hydrocarbon cracking; (ii) discharge drive frequency and plasma space time have a big effect on the H2 specific energy requirement (SER) and H2 generation rate, respectively; (iii) feedstock chemistry affects the H2 and C2 products observed; (iv) carbon particulates rapidly form in the liquid hydrocarbon, but they can be separated easily; and (v) the SER for H2 production is 25-30 kWhr/kg, roughly two times less than water electrolysis in practice (60 kWhr/kg). Hydrocarbon conversion, reaction rates, and characterization of the plasma (OES, high speed imaging), gas (MS), liquid (GC/MS), and solid phase (SEM, Raman) products as a function of plasma operating conditions (high and low AC drive frequency; liquid-plasma contact time) and hydrocarbon source will be discussed.
Structural Modification Strategy for Enhancing Electrochemical Performance of Electrodes Under High Current Cycling and First Principle Computational Research for Electrode Materials
Authors: Song Seunghyun , Kim Jihyun , Vallem Sowjanya , LI Man , Cheng Xiong , Bae Joonho 
Published: August 2024

Recently, there has been significant interest in advancing lithium-ion battery technology due to its widespread use in various applications. Our research delves into this domain, focusing on enhancing the electrochemical properties of batteries through structural modification of electrode materials. Our work demonstrates the significant enhancements of electrochemical performance under high current cycling using structurally modified electrode materials . In first work, crumpled graphene oxide anode proves to be an effective strategy for enhancing its electrochemical properties, attributed to its advantageous crumpled morphology. This morphology allows for improved electrode stability and easier access for lithium ions, enabling them to interact with its larger specific surface area. In second work, we describe enhanced the drawback of reduced electrochemical performance during high-rate cycles by synthesizing multidimensional LFP-based carbon composite. The lithium ion diffusivity and electrode stability of the prepared composite are significantly improved in charging and discharging cycles by introducing graphene quantum dots alongside CNTs, exhibiting superior electrochemical properties even at high current densities. In third work, density functional theory simulation is employed for demonstrating the enhanced electrochemical properties of prepared electrodes by exploring their properties. Our research provides insights into electrode material design as an effective approach to enhancing the electrochemical properties of lithium-ion batteries.
Acknowledgement:
This work was supported by the National Research Foundation of Korea (NRF-2021R1A2C1008272). This work was supported by Ministry of Trade, Industry and Energy, KEIT, under the project title
"International standard development of evaluation methods for nano-carbon-based high-performance supercapacitors for electric vehicles" (project # 20016144).
Intergranular Shielding of Ultrafine-Grained Ni-Rich Layered Cathode for Advanced Lithium-Ion Batteries
Authors: Park Geon-Tae , Ryu Ji-Hyun , Sun Yang-Kook 
Published: August 2024

To achieve carbon neutrality on a global scale, fuel-powered vehicles are being steadily phased out over environmentally recommended electrified vehicles (EVs) with low greenhouse gas emissions. In a battery, the cathode is among the foremost components, as it predominantly determines the LIB’s performance and price. However, since current fleet of layered oxide NCM and NCA cathodes have a relatively lower Ni content, they can extract only a limited amount of reversible capacity (210 mAh∙g-1), restricting the driving range of EVs. To achieve higher energy densities, many studies have focused on increasing the average fraction of Ni in NCM or NCA cathodes to more than 90%. However, the extraction of large amounts of lithium ions is seriously compromised by the rapid deterioration of both cycle life and thermal safety. Recent studies on X-doped cathodes (X = B, Nb, Ta, Sb, W, and Mo) have offered promising results by engineering their geometric microstructural configurations to suppress intergranular cracking.1,2 This approach has proven its potential to improve the electrochemical cycling performance of Ni-rich NCA, NCM(A), and NM cathodes. However, prolonged exposure of the Ni-enriched (Ni ≥ 95%) cathode to the electrolyte generally results in continuous oxidative decomposition of electrolytes and subsequent cathode structural transformation, rendering the cathode unsuitable for applications requiring long battery life.3 Herein, we propose a highly stabilized Ni-enriched (Ni ≥ 95%) layered cathode by adopting a multi-stage engineering strategy, i.e., the construction of an ultrafine-scaled microstructure and subsequent intergranular shielding of the refined grains. The formation of an F induced protective layer at the intergranular boundaries of the ultrafine grains in Li[Ni0.95Co0.04Mo0.01]O2 (denoted as Mo1-NC96) noticeably improved both the structural and chemical stability of the cathode, with a limited degree of structural degradation and gas evolution.

Reference
s
:

[1] U.-H. Kim, G.-T. Park, B.-K. Son, G.W. Nam, J. Liu, L.-Y. Kuo, P. Kaghazchi, C.S. Yoon, Y.-K. Sun, Nat. Energy, 5 (2020) 860-869.
[2] G.-T. Park, B. Namkoong, S.-B. Kim, J. Liu, C.S. Yoon, Y.-K. Sun, Nat. Energy, 7 (2022) 946-954.
[3] F. Kong, C. Liang, L. Wang, Y. Zheng, S. Perananthan, R.C. Longo, J.P. Ferraris, M. Kim, K. Cho, Adv. Energy Mater., 9 (2019) 1802586.
Simulation of Magnetic Separation of Metal Ions in Aqueous Electrolytes
Authors: Carlstedt Nicholas , Andrei Petru 
Published: August 2024

The magnetic separation of metal ions provides an alternative solution to traditional separation techniques such as pyrometallurgy, hydrometallurgy, biometallurgy or electrodialysis. Compared to traditional techniques that either use large amounts of chemicals (usually inorganic acids combined with reducing agent), produce large amounts of sludge as solid waste, consume a large amount of energy, or are difficult to separate ions of different charges [1], the magnetic separation of the metal ions can separate ions based on their magnetic susceptibility. This method is environmentally friendly [2] and consumes a small amount of energy (particularly when the system is designed using permanent magnets instead of electromagnets). The goal of this presentation is twofold. First, we derive the set of transport equations that need to be used to simulate the magnetic separation of metal ions in aqueous solutions. Then, we use these transport equations to simulate the magnetic separation process in various magnetic systems and predict the efficiency of magnetic separation of different systems.
The mathematical model developed here is based on coupling the three-dimensional Navier-Stokes equations for flow transport with the drift (migration)-diffusion equations of ion transport [3] in the presence of magnetic field gradients. Both the drift-diffusion model and the Navier-Stokes equations include the magnetic force term as an additional driving force. By solving the entire system of equations self-consistently we analyze the effect of the diffusivity, concentration gradients, magnetic field gradients and fluid velocity over the capturing properties of the system. A detailed presentation of the mathematical model, underlying assumptions of the model, limiting cases, numerical implementation in three-dimensional structures, and simulations results will be presented at the meeting. In addition, we will present predictions for the magnetic separation of Li, Fe, Ni, Mn, and Co from the solution phase. Fortunately, these ions have significantly different magnetic susceptibility, which vary over more than 3 orders of magnitude, and which allows for the efficient extraction and separation of the elements from the solution and from each other.

References:

[1] K. H. Chan, M. Malik, and G. Azimi, “Separation of lithium, nickel, manganese, and cobalt from waste lithium-ion batteries using electrodialysis,” Resour. Conserv. Recycl., vol. 178, p. 106076, Mar. 2022, doi: 10.1016/j.resconrec.2021.106076.
[2] Z. Lei, B. Fritzsche, R. Salikhov, K. Schwarzenberger, O. Hellwig, and K. Eckert, “Magnetic Separation of Rare-Earth Ions: Property Database and Kelvin Force Distribution,” J. Phys. Chem. C, vol. 126, no. 4, pp. 2226–2233, Feb. 2022, doi: 10.1021/acs.jpcc.1c09748.
[3] J. Newman and K. Thomas-Alyea, Electrochemical Systems, 3rd Edition. John Wiley&Sons, 2004.
(Invited) Doping at the Extreme in Organic Semiconductors: Challenges and Opportunities
Authors: Kahn Antoine 
Published: August 2024

Molecular doping is an effective tool to enhance bulk conductivity, increase carrier injection and de-activate electron or hole traps in organic molecular and polymer semiconductors. Considerable effort has been directed toward the synthesis of powerful and stable p-type and n-type molecular dopants over the past decade.[1,2] This talk reviews a range of molecular redox agents used in organic electronics, with focus on strong reductants and oxidants for organic semiconductors with low electron affinity (EA) and large ionization energy (IE), respectively. In particular, we look at air-stable dimers, e.g. [RuCp*Mes]2, formed of 19-electron organometallic sandwich compounds able to reduce organic semiconductors with EA well below 3 eV.[3] We review powerful single-electron molecular oxidants, e.g. F6-TCNNQ and CN6-CP, which can introduce holes in organic semiconductors with IE larger than 5.6 eV. Applications of these n- and p-dopants to improve the conductivity of carrier injection layers and create large gap semiconductor p-i-n structures are described.[4] The last part of the talk focuses on recent work on adduct-based p-doping of organic semiconductors, applicable to a range of hole transport materials.[5]
[1]S. Barlow, S.R. Marder, X. Lin, F. Zhang and A. Kahn, Electrical Doping of Organic Semiconductors with Molecular Oxidants and Reductants, Handbook of Conducting Polymers (2019)
[2] G. Song, S.B. Kim,S. Mohapatra, Y. Qi, T. Sajoto, A. Kahn, S.R. Marder, S. Barlow, n-Doping of Organic Electronic Materials Using Air-Stable Organometallics, Adv. Mat. 24, 699 (2012)
[3] X. Lin, B. Wegner, K. M. Lee, M. A. Fusella, F. Zhang, K. Moudgil, B. P. Rand, S. Barlow, S. R. Marder, N. Kochand A. Kahn, Beating the Thermodynamic Limit: Photo-Activation of n-Doping in Organic Semiconductors, Nature Materials 16, 1209 (2017)
[4] H. L. Smith, J. T. Dull, S. Mohapatra, S. Barlow, S. Marder, B. P. Rand, and A. Kahn, Powerful organic molecular oxidant and reductant enable a large gap, blue light-emitting organic homojunction diode, ACS Appl. Mat. Int. 14, 2381 (2022)
[5] N. Sakai, R. Warren, F. Zhang, S. Nayak, S. V. Kesava, Y.-H. Lin, H. S. Biswal, X. Lin, A. Kahn, M. Riede, P. K. Nayak and H. J. Snaith, Adduct-based p-doping of Organic Semiconductors, Nature Materials, 20, 1248 (2021)