bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrodeposited Lithiophilic Zn Thin Film on the Current Collector for Improved Cyclability of Anode-Free Lithium Metal Battery
Authors: Afzali Pooria , Magagnin Luca 
Published: February 2024

Anode-free lithium metal batteries (AFMBs) are recently presented as the new generation of Li metal batteries benefiting high gravimetric and volumetric energy densities due to the zero excess lithium. However, poor electrochemical stability and maximum cyclability of around 40-50 cycles due to the zero excess Lithium prevent the AFLMBs to be functional1. Here, lithiophilic electrodeposited Zn thin film on the current collector is reported in order to decrease the lithium nucleation overpotential and improve the plating/stripping process during alloying and dealloying. Moreover, columbic efficiency is increased by applying more zinc coated on the cupper current collector and by providing a more hospitable site for Li nuclei to plate2. Due to the alloy formation of Li-Zn, more conformal Li growth on the current collector is provided and homogeneous Li distribution and smooth morphology are observed by SEM images. The cells in different zinc thin layer coating are cycled with different current densities as well as long-term cycling by galvanostatic cycling charge-discharge cycling. As a result, increasing the thin film thickness up to 1 micron significantly enhances the electrochemical stability of the cells such as higher columbic efficiency and cyclability, lower Li nucleation overpotential. Finally, the Li-ion chemical diffusion coefficients DLi, are evaluated by galvanostatic intermittent titration technique (GITT) and electrochemical impedance spectroscopy (EIS) and the results are compared to each other3.
References

Maddukuri, S. et al. On the challenge of large energy storage by electrochemical devices. Electrochim Acta
354, 136771 (2020).

Merso, S. K. et al. An in-situ formed bifunctional layer for suppressing Li dendrite growth and stabilizing the solid electrolyte interphase layer of anode free lithium metal batteries. J Energy Storage
56, 105955 (2022).

Xie, J. et al. Determination of Li-ion diffusion coefficient in amorphous Zn and ZnO thin films prepared by radio frequency magnetron sputtering. Thin Solid Films
519, 3373–3377 (2011).
Heterointerface-Induced Fast Na+ Transport of Sn Anode Using a Yolk-Shell Structure for Fast-Charging and Stable Sodium-Ion Batteries
Authors: Lim Hyojun , Kim Sang-Ok 
Published: February 2024

Sodium-ion battery (SIB) is a promising next-generation secondary battery system that uses inexpensive sodium resources, which can lower battery production costs. Moreover, based on similar chemical and electrochemical reaction mechanisms as conventional lithium-ion battery (LIB), it is expected that technology development can be rapidly achieved by utilizing existing battery manufacturing processes. However, because of the larger ionic radius (1.02 Å) and weight of sodium compared to those of lithium (0.76 Å), SIBs inevitably have lower energy and power densities compared to LIB. Therefore, to address these challenges, developing suitable host material with superior electrochemical performance (high capacity/high power density/long cyclability) is urgently required.
In this regard, metallic Sn has attracted attention as a promising anode material with a high theoretical capacity of 870 mAh/g through the reversible electrochemical (de)alloying reaction with sodium, which could overcome the low energy density limit of hard carbon anode. Nevertheless, due to the interfacial instability of Sn particles upon cycling and the slow alloying reaction rate during the sodiation process, the Sn anode exhibits poor rate performance and insufficient long-term cycling stability. Additionally, the structural degradation caused by significant volume variations further limits its practical implementation in SIBs.
Here, to solve the above issues, we propose a hierarchically designed composite anode consisting of Sn yolk and multifunctional C/SiOC shell (denoted as Sn@C/SiOC) via a simple pyrolysis method using the suspension of the Sn precursor in silicone oil. We conducted various physical, chemical, and electrochemical characterization, and we further carried out an in-depth investigation including post-mortem and in-situ EIS analyses to reveal the heterointerface-induced improved sodium-ion storage performance. We expect that the heterointerface modification strategy will contribute to the realization of advanced electrode materials in SIBs and other next-generation energy storage devices.
MOCVD of ZrN: Tuning Thin Film Properties Towards Catalytic Applications
Authors: Glauber Jean-Pierre , Liu Ji , Lorenz Julian , Bragulla Sebastian , Müller Björn , Harms Corinna , Wark Michael , Nolan Michael , Devi Anjana 
Published: February 2024

Transition metal nitrides (TMN) have gained increasing attention over recent years as active materials for energy related applications including catalysis and energy storage. They feature high electrical conductivities, wide optical band gaps and superior chemical stability.[1] In particular, ZrN has been recently identified as a promising material for a range of potential applications that include plasmonic devices,[2] as a catalyst for the oxygen reduction reaction (ORR),[3] and as a catalyst for the nitrogen reduction reaction (NRR),[4] due to its appealing electronic properties, while being cheap and abundant compared to commonly used noble metals.[1,5] The fabrication of ZrN on large scale under moderate process conditions, with the required properties for catalytic applications, motivates the use of chemical vapor deposition (CVD) as the method of choice. Moreover, with the variation of process parameters that includes precursor choice and growth temperature, it is possible to tune the surface features as well as composition of the layers that are suitable for catalytic applications.
In this study, we have employed metal organic chemical vapor deposition (MOCVD) to synthesize ZrN layers on Si and glassy carbon (GC) substrates in the temperature range of 550 – 850 °C. The influence of the nature of the precursor and deposition temperature on the structure, composition and surface morphology of the ZrN layers was systematically studied. Oriented ZrN layers with facetted grain morphology were obtained. ZrN films of different thickness were analyzed by complementary methods including X-ray diffraction (XRD) (Figure 1 a)), Raman spectroscopy, Rutherford backscattering spectrometry (RBS) (Figure 1 b)), nuclear reaction analysis (NRA), scanning electron microscopy (SEM) (Figure 1 c)), and X-ray photoelectron spectroscopy (XPS). Based on the detailed film analysis, catalyst surfaces were modeled by DFT calculations. The NRR activity and selectivity towards the competing hydrogen evolution reaction (HER) were evaluated by first principles simulations and electrochemical experiments. This preliminary study on material fabrication and theoretical investigations lays a foundation for the investigation of ZrN for NRR applications for future studies.
References:
[1]: Luo, Q.; Lu, C.; Liu, L.; Zhu, M., Green Energy &
Environ.
2023 8 (2), 406.
[2]: Shabani, A.; Tsegay K., M.; Petersen, S.; Khazaei N., M.; Kumar M., Y.; Adam, J., Adv Photo Res. 2021 2 (11), 2100178.
[3]: Yuan, Y.; Wang, J.; Adimi, S.; Shen, H.; Thomas, T.; Ma, R. et al., Nat. Mater.
2020, 19 (3), 282.
[4]: Abghoui, Y.; Garden, A. L.; Howalt, J. G.; Vegge, T.; Skúlason, E., ACS Catal.
2016 6 (2), S. 635.
[5]: Xie, J.; Xie, Y., Chemistry
2016, 22, 3588.

Figure 1
(Invited) Organic Polymer Dots for Photocatalysis
Authors: Tian Haining 
Published: February 2024

Organic polymeric photocatalysts have been attracted scientists’ interests during past years due to their low-cost, tunable bandgaps and energy levels, and promising photocatalytic performance. Making the traditional hydrophobic polymeric photocatalyst into nano-particles with size less than 100 nm, so-called polymer dots (Pdots), has shown significantly enhanced photocatalytic activity. Rational design of organic polymers is one of strategies to improve photocatalytic performance for hydrogen production. Moreover, making heterojunction Pdots can efficiently separate photogenerated charges within Pdots as well as utilize energy transfer process to enhance the light harvesting efficiency. In this talk, I will discuss our research achievements in optimization of polymer structures on Pdots photocatalysis, study of photocatalytic mechanism in heterojunction Pdots systems and applications of Pdots in bio-hybrid photocatalytic systems.
Relevant publications:
[1] Wang L., et al., Angew. Chem., 2016, 128 (40), 12494-12498
[2] Pati P., et al., Energy Environ. Sci., 2017 10 (6), 1372-1376
[3] Liu A., et al., J. Am. Chem. Soc., 2021, 143 (7), 2875-2885
[4] Pavliuk M., et al., J. Am. Chem. Soc. 2022, 144(30) 13600–13611
[5] Wang S., et al., Angew. Chem. Int. Ed., 2022, 61(23), e202202733
Solar Water Splitting Device Integrated Carbon-Based Electrodes and Carbon-Based Perovskite Solar Cells
Authors: Tsuji Ryuki , Ito Seigo 
Published: February 2024

Producing hydrogen from integrated devices by solar-driven water splitting (SWS) is one of the most attractive methods for renewable energy conversion. However, their widespread use is hindered by their cost and poor performance. In this work, we developed an integrated device consisting of three series-connected carbon-based multi-porous-layered-electrode perovskite solar cells (MPLE-PSCs) 1-5 and carbon-based catalyst-decorated electrode couples (Figure 1a). Porous carbon electrodes with a graphite and carbon black mixture are used for the back contacts of solar cells, and pencil-lead graphite rods (PGRs) are used as electrocatalyst supports for water-splitting cells, which are much cheaper than existing materials. The performance of the PSC was compared between the 2 and 3-series, and the performance of the water-splitting cell with/without catalyst. In addition, each combination was compared.
The solar to electricity efficiency (STE, same as power conversion efficiency: PCE) was 13.79% and 13.16% for the 2-series and 3-series, respectively. The electricity to hydrogen efficiency (ETH), calculated as V
theoritical/V
operating, 6 was 78.34% and 84.83%, for PGR and NiFe/PGR respectively. Furthermore, the matching factor (MF), calculated as (V
operating × J
operating)/(V
max × J
max), 6 for the <2-series PSCs>/<PGR> combination and the <3-series PSCs>/<NiFe/PGR> combination were 48.57% and 83.77%, respectively. Solar to hydrogen efficiency (STE), calculated as STE ×ETH × MF, improved from 5.25% to 9.35% for the optimized device (Figure 1b). These results show that low-cost and high-efficiency solar hydrogen can be produced by using Earth-abundant materials and by adjusting the maximum output of the device.
(1) A. Mei, et al., Science
345, 295 (2014).
(2) R. Tsuji, et al., Electrochemistry
88, 418 (2020).
(3) R. Tsuji, et al., Photonics
7, 133 (2020).
(4) D. Bogachuk, R. Tsuji, et al., Carbon
178, 10 (2021).
(5) E. Kobayashi, R. Tsuji, et al., Cell Rep. Phys. Sci.
2, 100648 (2021).
(6) Z. N. Zahran, et al., ACS Appl. Energy Mater.
5, 8241 (2022).
Figure 1. Carbon-based solar water splitting. (a) Schematic diagram and (b) J-V curves of MPLE-PSCs and LSV curves of water electrolysis with PGR electrodes.

Figure 1
(Invited) Integration of Sulfide and Halide Based Solid-Electrolyte Membranes with Li-Ion Cathodes
Authors: Nanda Jagjit 
Published: February 2024

Lithium metal-based batteries (LMBs) employ a Li-metal anode coupled with a conventional high voltage ceramic cathode. The higher capacity of Li vs. graphite (3861 mAh g-1
vs. 372 mAh g-1) combined with high voltage cathodes results in an over 50% increase in the specific energy versus conventional ion-insertion anodes. All-solid-state batteries (ASSBs) can achieve the sought-after high energies when employing cathodes such as LiNi0.8Mn0.1Co0.1O2 (NMC811) and LiNi0.5Mn1.5O4. Having the SEs be as thin as practically possible maximizes the energy density of the cells by both reducing the total weight and achieving voltage window closer to the theoretical limit due to reduced impedance. Likewise, a thin metal anode is sought-after since it reduces the cell weight as well as the risk associated with accidental ignition of the metal. Argyrodite SEs such as Li6PS5Cl (LPSCl) and Li6PS5Br (LPSBr) form terminal decomposition products such as Li3P and Li2S at the metal anode. However, it is the presence of halide-based decomposition products such as LiCl that kinetically stabilizes the interface. For example, substantially improved ASSB performance has been achieved with “sandwich” structures such as LPSCl/LGPS/LPSCl.
The talk will focus on the recent approaches to improve interfacial stability of sulfide based solid electrolytes (SEs) with Li-metal and NMC based cathodes for SSB’s. A comparative evaluation of SSB performance between Argyrodite (Li6PS5X, X= Cl, Br) and halide-based SE (Li3ACl6, A = In, Y) using them as a separator and catholyte will be presented. Overall, these results demonstrate that incorporating oxidatively stable SEs in composite cathodes does not necessarily ensure the formation of robust NMC/SE interfaces, and cumulative irreversible capacity losses in such cells can yield rapid performance decline. Rather than SE decomposition, the dominant cause for capacity fade in SSBs is due to active material isolation resulting from repeated volume changes during cycling. Further, additional understanding of the mechanics of solid-solid interfaces and their dynamical evolution during SSB operation will be critical to address key performance bottlenecks for Li metal SSBs.
A Glass-Interphase for Highly Reversible and Stable RT-Na/S Batteries
Authors: Soni Chhail Bihari , Soni Chhail 
Published: February 2024

Owing to the high theoretical specific capacity (1165 mA h g-1), high natural abundance, and low redox potential (-2.71 V vs standard hydrogen electrode), sodium metal is considered as an ideal anode material for the next-generation high-energy batteries. Though, a high-temperature variant of the sodium-sulfur batteries has already been commercialized, its compromised safety (due to high-temperature operation, 250 – 300 ⁰C) has triggered the research interest in developing its room-temperature analogue. At room-temperature, the thermodynamic instability of Na metal with the liquid electrolytes often leads to develop a thick and chemically unstable interphase, often called the solid electrolyte interphase (SEI). Upon Na plating/stripping, the SEI grows and dissolves repeatedly, results in consuming both the Na anode and the electrolyte inventory. The Na dendrites, the primary unknown risk associated with Na metal-based batteries, are inclined to develop from the fractured sites of the SEI. The SEI exfoliation can be attributed to weak chemical adhesion between the SEI and the Na metal anode. Functional additives, engineered solvents, and the high concentration electrolytes have often been used to alter the mechanical and electrochemical properties of the SEI. It is apparent that, a stable and durable SEI is the key to creating a secure, dendrite-free, and long-lasting RT-Na/S batteries.
More recently, the idea of glass-electrolytes to stabilize the metal anodes is disclosed by the Nobel laureate Prof. J. Goodenough. The glass-electrolyte is used to suppress the dendrite growth and ensured improved safety of the high-energy metal-sulfur batteries. However, the cell experiences a huge interfacial resistance due to metal anode/glass-electrolyte interface.
The present work relates to the development of a glass-interphase for RT-Na/S batteries. The interphase is grown directly over the sodium metal anode through a simple and scalable approach. To growth the interphase, a novel organic molecule is used to facilitate the formation of the glass-interphase, and called as “glass-interphase forming additive (GIFA). In general, GIFAs contains the hydrolysable group, which is commonly an amine, acyloxy, alkoxy, or halogen on one side, and one Si atom. It contains organo-functional group, such as epoxide, on other side. The presence of oxide or hydroxide is essential in realizing interaction of GIFA with the sodium metal surface.
Overpotential Behavior of Electrolysis and Fuel Cell Modes of Molten Carbonate Cells
Authors: Lee ChoongGon , Koomson Samuel 
Published: February 2024

Molten carbonate is an high operating temperature electrolyte for the fuel cell (MCFC) and electrolysis cells (MCEC). In particular, the liquid molten carbonates allow the reversible operation between fuel cell and electrolysis cells. The electrode kinetics and mass transfer characteristics of MCFC have been rather extensively investigated compared with those of MCEC. In this work, the mass transfer behaviors between MCFC and MCEC have been focused by experimental way with 100 cm2 class bench cells.
The electrodes and matrix in the cell were supplied by KIST in Korea. The cells were operated at 923K under atmospheric pressure. The hydrogen electrode was supplied by a mixture of H2:CO2=1:1, 2:1, 1:2 ratios at 20% or 40% H2O. The oxygen electrode was fed by Air:CO2=0.7:0.3 atm. The steady state polarization (SSP) from 0 to 150 mA cm-2, inert gas step addition (ISA), and reactant gas addition (RA) methods were employed. The ISA adds inert gas to the hydrogen or oxygen electrodes, then the addition varies reactants flow rate and partial pressures. Consequently, the variations are reflected to the cell voltage at open circuit and polarization states. The voltage shift by the flow and partial pressure change represents overpotential behaviors at the electrodes [1]. The RA method uses a reactant gas instead of inert gas in the ISA. Therefore, the RA provides the overpotential information of the added reactant species [2].
From the experimental investigations, the total voltage loss at the FC is larger than that of EC mode. In addition, the hydrogen electrode has significant gas phase mass transfer resistance due to the H2, CO2, and H2O species at the FC and EC modes. A similar overpotential was observed at the hydrogen electrode. On the other hand, the oxygen electrode has much less overpotential at the EC mode than the FC mode. Since the oxygen reduction at the FC mode contains O2 dissolution and mass transfer through the carbonate electrolytes, liquid phase mass transfer resistance is dominant. However, the oxidation of carbonate ions to oxygen does not contain liquid phase mass transfer process at the EC mode. Therefore, much less overpotential was observed at the oxygen electrode at the EC mode than the FC mode. This can be a reason of smaller total voltage loss at the MCEC than the MCFC.
[1] Samuel Koomson, Choong-Gon Lee, J. Electroanalytical Chemistry, 925, 116896 (2022).
[2] C.-G. Lee, H.-C. Lim, J. Electrochem. Soc., 152, A219-A228 (2005).
Polymeric Anion Exchange Membranes for Green Hydrogen Production
Authors: Roggi Andrea , Martinelli Elisa 
Published: February 2024

Producing green hydrogen by using anion exchange membrane (AEM) water electrolysis is a promising approach to address the severe climate and energy crisis facing human society and aid the transition to net-zero emissions. AEM electrolysis can be integrated with renewable energy sources and utilizes cost-effective (Pt-free) electrocatalysts and other inexpensive components in stacks. To enable commercially viable hydrogen generation, improvement of the AEM component is imperative, and the goal of fabricating a membrane, in which the chemical, mechanical and electrochemical requirements are combined and optimized in a synergistic way, still represents a challenging task.The present work was, therefore, aimed at addressing several unique features of AEMs for implementation in an industrially scalable and sustainable energy-production process through a suitable synthetic strategy that involves the post-modification of a commercially available and relatively cheap poly(styrene-b-butadiene) (SB)-based block copolymer matrix by grafting vinylbenzyl chloride (VBC). The synthesized SB-g-VBC copolymers were, therefore, used for the fabrication of AEMs by solution casting followed by quaternization reaction with trimethylamine (TMA) for the quantitative conversion of –CH2Cl into –CH2(CH3)3N+ groups. Obtained AEMs were thermally, mechanically and electrochemically characterized. By varying the VBC functionalization degree of the copolymers it was possible to modulate the ionic exchange capacity, conductivity, water uptake and mechanical properties of the membranes derived therefrom. The most promising AEMs were selected for testing in electrolytic cells (Figure 1) and were found to resist to real operating conditions for more than 40 days.

Acknowledgements. The authors thank the company Enapter s.r.l. for the contribution to the electrochemical characterization and the financial support.
Figure.1 Polarization curves of the SB-g-VBC based AEM as a function of residence time in an electrolytic cell (KOH 1 wt % at 55 °C).

Figure 1
Metal−Organic Framework CPO-27 Derivatives As Non-Precious Metal Catalyst for Anion Exchange Membrane Fuel Cell
Authors: Pradesar Yusuf , Yusuf Afandi , Kabtamu Daniel Manaye , Wang Chen-Hao , Huang Hsin-Chih 
Published: February 2024

Fuel cell stands as an environmentally friendly technology harnessing the power of hydrogen to generate clean water. In the range of fuel cell types, the anion exchange membrane fuel cell (AEMFC) stands out, effectively converting chemical energy to electricity without relying on platinum catalyst. Nonetheless, platinum catalyst is still used in addressing the sluggishness of the oxygen reduction reaction (ORR) during AEMFC operation. The scarcity and expense of platinum, however, hinder its widespread adoption. Furthermore, in the alkaline environment, platinum surface is covered with OH species, impeding active sites and diminishing electrochemical activity. Consequently, seeking an efficient, stable, and abundant platinum substitute is a primary target in the development of fuel cell.
This study focuses on the development of the non-precious metal catalyst for the ORR in AEMFC. The catalyst, denoted as NiCo2-CPO-27/PCN, is derived from a carbon nanorod structure obtained from the metal-organic framework (CPO-27). Through the optimized process, the catalyst demonstrates the distinct carbon nanorod configuration. Additionally, the NiCo2-CPO-27/PCN catalyst exhibits enhanced ORR activity, achieving the electron transfer number of 3.99, which closely approaches the ideal four-electron transfer number. This improvement in activity is attributed to factors such as the specific structure, heteroatom contribution, and coordination arrangement of the catalyst.
Growth of Medium-Sized InP Quantum Dots with High Photoluminescence Efficiency and Enhanced Stability
Authors: Yi-Jui Ho , Cheng-Yang Chen , Chen Hsueh-Shih 
Published: February 2024

This study introduces medium-sized core/shell InP quantum dots (QDs) with high photoluminescence (PL) efficiency and remarkable material stability. The incorporation of a ZnSe interlayer between the core and the thicker outer ZnS shell enhances both the optical performance and material stability. When further increasing the S/Se ratio to synthesize larger QDs with a thicker ZnS layer, optical performance significantly declines despite the improvement in stability. To achieve QDs with superior optical performance and stability, we controlled the S/Se ratio variation during shell growth and examined its impact on the structure, morphology, and size of InP QDs. Our approach resulted in medium-sized InP/ZnSe/ZnS QDs with tunable wavelengths (606-630 nm), PL quantum yields (PLQY) > 90%, full width at half maximum (FWHM) values < 40 nm, and enhanced material stability.
Keywords: indium phosphide (InP), quantum dots (QDs), high efficiency and stability, S/Se ratio of shell, medium-size quantum dots, stainless steel reactor

Figure 1