bluuebunny/crossref_metadata_2025_split huggingface dataset:
Investigating the Impact of Si/C Supraparticles Size Distribution on the Lifetime of Li-Ion Battery Half-Cells
Authors: Amin Adil , Loewenich Moritz , T. Kahl Julius , Kräenbring Mena-Alexander , Wiggers Hartmut , Özcan Fatih , Segets Doris 
Published: February 2024

The development of high-performance anodes for lithium-ion batteries (LiBs) with robust cycling stability has become a prominent area of research. In our recent study (Amin et al. 2023), we demonstrated that adopting a hierarchical structuring strategy via spray drying can significantly improve the cycle life of silicon-based anode materials in contrast to their nanoparticle building blocks (4 wt.% of compounding carbon). This method enhances the structural stability of the anode, thereby improving cyclic performance and paving the way for the development of high-capacity LIBs.
However, beyond phenomenological proof of principles, understanding the effect of supraparticles size distribution on electrochemical performance is of great significance for making Si-based active materials ready for the LiBs industry. Therefore, we systematically investigated the correlations between supraparticle median sizes/size distributions and other supraparticle properties such as their BET surface area, slurry rheology, coated layer quality, and the electrochemical Coulombic efficiency of half-cells. These findings revealed that supraparticles with large median sizes are stable against processing as compared to small size supraparticles as can be seen from atomic force microscopic (AFM) images of coated layers in Fig 1a. It is also discovered that large supraparticles enhance the 3rd cycle Coulombic efficiency (2 formation cycles) of Li-ion half cells at 0.5 C as shown in Fig.1b. However, there exists an optimal median size/size distribution above which the Coulombic efficiency and cycling stability of the supraparticles in half-cells starts to decrease.
In short, supraparticles exhibit properties (e.g., high layer stability, low surface reactions) that outperform those of individual nanoparticles. Understanding the role of supraparticle sizes in generating anodes with a hierarchical structure demonstrates great promises towards tailored materials for enhanced LiB performance. This enables us to further unravel process-structure-property relationships and understand the physics behind the improved electrochemical performance of supraparticles.

Publication bibliography

Amin, Adil; Loewenich, Moritz; Kilian, Stefan O.; Wassmer, Theresa; Bade, Stefan; Lyubina, Julia et al. (2023): One-Step Non-Reactive Spray Drying Approach to Produce Silicon/Carbon Composite-Based Hierarchically Structured Supraparticles for Lithium-Ion Battery Anodes. In J. Electrochem. Soc. DOI: 10.1149/1945-7111/acb66b.

Figure 1
Identification and Quantification of Lithium Ion Battery Electrolyte Residues in Blackmass Via Headspace-GC-MS/FID
Authors: Hesper Jakob Michael , Winter Martin , Nowak Sascha 
Published: February 2024

Due to the increasing demand for lithium-ion batteries (LIBs) in recent years, the demand for resources has also risen. As a result, the amount of LIBs that have reached the end of their life is increasing, leading to stricter guidelines that require certain proportions of recycled materials in the production of new LIBs. Typical recycling strategies start by deactivating, dismantling and shredding LIBs, thereby generating blackmass consisting of active and inactive materials (e.g. Li, Mn, Ni, Co, Cu and organic carbonates). However, black mass is a non-standardized resource, and its composition and purity vary depending on the respective process. 1,2 Therefore, it is essential to characterize and quantify its composition in order to make use of this highly variable resource stream while maintaining quality and safety.
This work aims to identify and quantify organic electrolyte residues in black mass without further sample preparation. To achieve this, the samples were agitated using a headspace sampler and then analyzed by gas chromatography-mass spectrometry (GC-MS) and flame ionization detector (FID). Linear and cyclic carbonates such as dimethyl carbonate, ethyl methyl carbonate, and ethylene carbonate, as well as aging products such as 2,5-dioxahexanedioic acid dimethyl ester (DMDOHC), were detected. The identification results were compared to those achieved by thermodesorption and solid-phase microextraction.
Overall, this study demonstrates a method for identifying and quantifying organic electrolyte residues in black mass, which can aid in the development of more efficient and sustainable recycling processes for LIBs.
References
(1) Peschel, C.; van Wickeren, S.; Preibisch, Y.; Naber, V.; Werner, D.; Frankenstein, L.; Horsthemke, F.; Peuker, U.; Winter, M.; Nowak, S. Comprehensive Characterization of Shredded Lithium-Ion Battery Recycling Material. Chemistry (Weinheim an der Bergstrasse, Germany)
2022, 28, e202200485.
(2) Neumann, J.; Petranikova, M.; Meeus, M.; Gamarra, J. D.; Younesi, R.; Winter, M.; Nowak, S. Recycling of Lithium‐Ion Batteries—Current State of the Art, Circular Economy, and Next Generation Recycling. Advanced Energy Materials
2022, 761, 2102917.
A Cu-Containing High-Entropy Alloy with High Corrosion Resistance and Low Surface Electrical Resistance
Authors: Fujiwara Natsumi , Muto Izumi , Nishimoto Masashi , Sugawara Yu 
Published: February 2024

Cu-base alloys with high corrosion resistance and low surface electrical resistance in corrosive environments were studied for application to electrical connectors. To achieve both high corrosion resistance and low surface electrical resistance, duplex alloys were fabricated.
Non-equiatomic CuSnZnAlNi high-entropy alloys were prepared by induction melting. As raw materials, Cu-Zn alloy and pure metals of Sn, Al, and Ni were used. After casting, heat treatment was performed at 500 ℃ for 5 h (water-quenching). After that, the specimen surfaces were polished with a diamond paste down to 1 µm. The microstructure of the specimens was observed using an optical microscope and a field emission scanning electron microscope (FE-SEM) equipped with energy dispersive X-ray spectroscopy system (EDS). Electrochemical measurements were performed in synthetic seawater (pH 8.2) at 25 ℃. Dip-dry corrosion test was conducted. The specimens were dipped in synthetic seawater (pH 8.2) for 3.5 h and dried at 25 ℃ and 30 %RH for 0.5 h. Before and after the dip-dry corrosion test, surface electrical resistance was measured.
Cu36Sn16Zn16Al16Ni16 was prepared, and the phases were identified by SEM/EDS. As a result, the alloys were separated into four phases. The corrosion resistance of each phase was compared by SEM/EDS between the specimens before polarization and the specimens after polarization and removal of corrosion products. 20 cycles of dip-dry corrosion test was conducted, with one cycle being the combination of immersion of the specimen in the solution and drying.
The Trade-Off Relationship between Particle Proximity Effect and Low-Pt Loading to Optimize Oxygen Reduction and Methanol Oxidation Reaction Activity
Authors: Cheng Jiarun , Geng Dongsheng 
Published: February 2024

Pt-based electrocatalysts have long been considered as the most effective oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) catalysts due to their excellent intrinsic activity. For supported catalysts, Pt loading, particle size, interparticle distance (ipd), and interaction with support are identified as key contributors for high activity and selectivity. The proximity effect is a relatively new topic in catalysis research. There is a contradiction between the traditional view which induces the electronic interaction to reduce the activity and the new view which causes the electrical double-layer overlap of adjacent nanoclusters, changes the potential distribution and improves the specific activity. [1, 2]
To this end, we have developed the nitrogen-doped graphite-like carbon sheets supporting low-Pt loading (Pt@N-GC) with uniform sizes and controllable ipd, and disentangled the main effect of ipd on ORR activity/selectivity and MOR activity/CO tolerance. Combining electrochemical tests and the trade-off mechanism between proximity effect and low-Pt loading, the following trends were obtained:
1) 10.0 wt% Pt@N-GC with highest Pt loading and lowest ipd inhibits 2e- ORR by strong adsorption and reabsorption of *OOH due to the presence of closer Pt sites, and improves 4e- ORR selectivity. However, the mass activity/specific activity reached the maximum under the optimal low-Pt loading of 5.0 wt%.
2) Similarly, 10.0 wt% Pt@N-GC weakened the adsorption of the -OH group of oxidized COads intermediates, led to the strong adsorption of COads on the catalyst surface, inactivated of Pt sites and reduced the CO resistance. Considering the need to improve CO tolerance while increasing MOR activity, the 5.0 wt% low-Pt loading catalyst exhibiting the best MOR performance under the optimal ipd.
3) Benefiting by the synergistic effect of Pt nanoparticles and N-GC support, all Pt@N-GCs exhibit bifunctional electrocatalytic activity and durability.
We attribute these findings to the underlying mechanism trade-off between the particle proximity effect and low-Pt loading under the uniform particle size and controlled ipd (Figure. 1). We believe the proximity effect has positive and negative effects, how to maximize the advantages of proximity effect can provide valuable guidance for the design and optimization of low-Pt loading bifunctional electrocatalysts in the future.
[1] M. Nesselberger, M. Roefzaad, R.F. Hamou, P.U. Biedermann, F.F. Schweinberger, S. Kunz, K. Schloegl, G.K. Wiberg, S. Ashton, U. Heiz, K.J. Mayrhofer, M. Arenz, Nat. Mater., 12 (2013) 919-924.
[2] M. Watanabe, H. Sei, P. Stonehart, J. Eelectroanal. Chem., 261 (1989) 375-387.

Figure 1. The trade-off mechanism analysis between proximity effect and low-Pt loading.

Figure 1
Preparation and Evaluation of Nafion/CeO2 Composite Electrolyte Membranes for Polymer Electrolyte Fuel Cells
Authors: Shudo Kazuki , Uchida Makoto , Kakinuma Katsuyoshi 
Published: February 2024

Polymer electrolyte fuel cells (PEFCs) are increasingly applied to the vehicles (FCVs) toward the suppression of carbon dioxide emission. The larger FCVs requires the high power density to exceed the presumed temperature limit of 80 ℃, causing some issues of material durability and system performances. In particular, a commercial electrolyte membrane of Nafion occurs the decrease of proton conductivity at the high temperatures under an atmospheric pressure. To overcome this problem, our research group has developed a composite electrolyte membrane consisting of Nafion and Ta-TiO2 nanoparticles with a chain-like network structure. The composite electrolyte membrane improves a proton conductivity in a wide temperature range over 100 ℃ by the effect of hydrophilic surface of the oxide. In this study, the other candidate materials of CeO2, nanoparticles with highly hydrophilic surface rather than that of Ta-TiO2 was selected to try to improve the proton conductivity of the composite electrolyte membranes.
The hydrophilic CeO2 nanoparticles with a chain-like network structure were prepared using flame oxide-synthesis method. The hydrophilic CeO2 nanoparticles were dispersed in a dispersion solvent in desired ratio. The dispersion was then added to 20 wt.% Nafion dispersion solution (DE2020 CS, Chemours Co.) neutralized with potassium hydroxide. The resulting dispersion was coated onto a die coater and dried using a hot air. The CeO2/Nafion composite membrane was then treated in high purified water with a sulfuric acid solution. The transmission electron microscopy (TEM) and water adsorption, and four-probe alternating current method was conducted to detect the microstructure, water uptake and proton conductivity of the composite membrane.
TEM images confirmed that the CeO2 nanoparticles were highly dispersed in the composite membrane. The proton conductivity of the 3 wt.% CeO2 containing composite membrane was 2.1 times higher than that of commercial Nafion membrane (NRE211, Chemours Co.) at 80 ℃, 20% RH, and was 1.5 times higher than that at 80 ℃, 80% RH (Fig. 1). The proton conductivity of the 3 wt.% CeO2 containing composite membrane was found to be higher than that of the Nafion monolayer in each water uptake (Fig. 2), indicating that the morphology of the membrane might be changed by the adding of CeO2 oxide. Further research will be needed to examine the proton conductivity mechanism of this composite membrane, and fuel cell evaluations using this composite membrane.

Figure 1
Electrochemical CO2 and CO Reduction with Size-Selected Nanoparticles
Authors: Sedano Varo Esperanza 
Published: February 2024

The development of efficient and selective catalysts for CO2 reduction (CO2R) is crucial for advancing the field of renewable energy and mitigating climate change. However, designing such catalysts is challenging due to the complexity of the CO2R process and the need for accurate modeling of catalyst behavior. Here, we present a novel experimental methodology that aims to bridge the gap between theoretical predictions and experimental observations to overcome these challenges.
To obtain the intrinsic activity and selectivity of CO2R catalysts, we deposited gas phase size-selected gold and copper nanoparticles on flat surfaces (glassy carbon) using magnetron sputtering. These nanoparticles were selected within an extremely low size range (around 0.1 nm) by using a Time-Of-Flight (TOF) mass filter, and deposited at very low loadings (less than 0.5 µg/cm2) to avoid aggregation. We then used a chip-based electrochemical mass spectrometry (EC-MS) setup, with approx. 8µL of stagnant electrolyte, for electrochemical test of the catalysts under operando conditions with a high degree of sensitivity.
Our findings reveal a non-linear relationship between the size of gold and copper nanoparticles and their selectivity for C+ products. Surprisingly, we found that both compositions exhibited an optimum size for C+ selectivity, which was not the largest size. By combining microscopy data with EC-MS results, we gained new insights into the intrinsic activity of size-selected nanoparticles and the factors that influence their selectivity.
Our methodology offers a promising approach for designing product-selective catalysts for CO2R. By defining experimental model systems, we were able to obtain the intrinsic activity and selectivity of these catalysts with reduced influence from external conditions. Our research makes a significant contribution to the development of sustainable energy solutions by providing experimental data that can inform theoretical models and guide the design of more efficient and selective CO2R catalysts.
A Robust Fuel Cell Operating on Lunar Water Derived Fuels
Authors: Rohde Sebastian , Gollas Bernhard , Cowley Aidan 
Published: February 2024

The space proven fuel cell technology will likely play a crucial role in the upcoming expansion of human presence into the solar system. In particular, polymer electrolyte membrane (PEM) fuel cells excel due to their high power-density, low weight and their ability to operate on in-situ resource utilization (ISRU) based fuels. Hydrogen fuel and oxygen can be derived from lunar water, which is believed to be trapped in permanently shadowed craters on the lunar poles. However, Colaprete A. et al. found that H2S and NH3 as well as smaller quantities of other sulfur compounds and hydrocarbons are detected alongside the water ice. These compounds are well known fuel impurities which cause reversible yet also irreversible damage to the platinum catalyst and other components of the membrane electrode assembly (MEA). Commercially available fuel cells on the other hand require highly purified fuels with contamination levels in the low ppb region. Thus, these impurities pose a profound problem, even if only a fraction of them is carried onwards to the hydrogen fuel and oxygen. Subsequent intensive purification processes are costly and require large amounts of energy – a process which could render the whole approach useless.
As mentioned before, H2S and other sulphur compounds adsorb strongly to the platinum metal and irreversibly degrade its catalytic activity until performance drops to unusably low levels. This effect is directly related to the amount of available catalyst, since a doubling of the platinum loading leads to a two-fold reduced degradation. We hypothesize that the resilience of a fuel cell can not only be improved by increasing the amount of platinum, yet also by using the available platinum more effectively. A lot of the platinum remains inactive within a fuel cell electrode due to different effects like excessive ionomer coverage or particle agglomeration. With the so-called platinum utilization parameter the obtained fuel cell performance is related to the total platinum weight and thus can be used to rate how effective platinum is used. In our recently published review, we found that electrospun electrodes have the highest platinum utilization out of all compared fuel cell electrode manufacturing methods. Furthermore, electrospun electrodes are reportedly less prone to other degradation mechanisms like Ostwald ripening. In this ongoing work, we aim to fabricate MEAs with fully electrospun electrodes and benchmark them against a commercial alternative. The electrodes will be operated with contaminated gases in half cell as well as full cell degradation experiments. The outcome of this research aims to support the exploration community in designing robust energy systems on the moon by investigating the effect of lunar contaminants on fuel cell systems.
(Invited) How, Where and Why Do and Should We Publish Our Findings?
Authors: Johansson Patrik 
Published: February 2024

Your publishing of your scientific findings has many facets; it is the publish-or-perish paradigm, it is a demand to get your degree, it is evaluated at all levels of your future carrier, etc. And surely you are also busy right now with writing your next manuscript to be submitted as soon as possible to a journal with an as high impact factor as possible? But as an early carrier researcher, why not already now stop and reflect a little on your own (future) publication pattern and habits? Have a solid re-think about it, come out more motivated and with a thought-through idea on who you want to be in the publishing landscape. And for those of you in the field of batteries, you will be armed with a bit of concrete input based on some statistics as well as guidelines.1-5

References

”Good practice guide for papers on batteries for the Journal of Power Sources”
Li, C. Arbizzani, S. Kjelstrup, J. Xiao, Y.-y Xia, Y. Yu, Y. Yang, I. Belharouak,
T. Zawodzinski, S.-T. Myung, R. Raccichini, S. Passerini,
J. Power Sources 2020, 452, 227824.

”An Experimental Checklist for Reporting Battery Performances”
Yang-Kook Sun, ACS Energy Lett. 2021, 6, 2187–2189.

”Standardized Battery Reporting Guidelines”
K. Stephan, Joule 2021, 5, 1–2.

”What can text mining tell us about lithium-ion battery researchers’ habits?”
El-Bouysidy, T. Lombardo, E. Primo, M. Duquesnoy, M. Morcrette, P. Johansson, P. Simon, A. Grimaud and A. A. Franco, Batteries & Supercaps, 2021, 4, 758-766.

”Ten Ways to Fool the Masses When Presenting Battery Research”
Johansson, S. Alvi, P. Ghorbanzade, M. Karlsmo, L. Loaiza, V. Thangavel, K. Westman and
F. Årén, Batteries & Supercaps, 2021, 4, 1785-1788.
(Invited) Anode and Cathode Self-Adhesive Ionomers for Durable Alkaline Water Electrolysis
Authors: Kohl Paul , Park Habin , Shah Parin 
Published: February 2024

Low-temperature water electrolysis using anion conductive polymer electrolytes has several potential advantages over acid-based polymer electrolyzers. However, the formation of durable, high surface area electrodes remains a challenge. The adhesion and connectivity of high surface area, particulate catalysts to the porous transport layer is critically important to the long-term cell lifetime. The water-fed, oxygen-evolving anode and dry hydrogen-evolving cathode has their own unique challenges in terms of catalyst adhesion, water uptake and ionic conductivity.
In this study, a family of covalently bonded, self-adherent, hydroxide conducting ionomers has been synthesized and tested under alkaline electrolysis conditions. The ionomers are based on hydroxide conducting poly(norbornene) terpolymers used in fuel cell and electrolyzers. Ionomers used in electrolysis electrodes must provide adhesion between the catalyst particles, porous transport layer and solid polymer membrane. Adhesion is especially important at the oxygen producing anode because of the intra-electrode forces created during the volumetric expansion of the liquid water into oxygen gas. However, the need for high ion conductivity is eased due to the supporting electrolyte in the water feed. The hydrogen-evolving cathode does not experience the same liquid-to-gas forces, but requires higher water uptake and ion conductivity because it is run without liquid or gas feed.
The terpolymer and tetrapolymer ionomers used in this work have been functionalized to provide cites for chemical bonding to the ionomer, catalyst, and porous transport layer. The resulting electrodes show excellent adhesion of the catalyst particles to the porous transport layer, as determined by adhesion and electrolyzer durability measurements. The anode and cathode ionomers have been customized for each electrode.
(Invited) Utilizing Conjugated Imine Polymers to Stabilize Nanoparticle Silicon Anodes
Authors: Martin Trevor R. , Rynearson Leah , Kuller Mackenzie , Quinn Joseph , Wang Chongmin , Lucht Brett L. , Neale Nathan R. 
Published: February 2024

Silicon anodes provide a compelling route towards delivering high-capacity lithium-ion batteries, however they are notoriously difficult to stabilize in conventional liquid electrolytes that are compatible with high performance cathodes. Furthermore, the drastic changes in volume that occur as silicon is lithiated and delithiated can lead to rapid cell failure and innovative polymeric binders are required to help mitigate mechanical issues. We have recently developed a novel method to synthesize the conjugated binder polyphenylmethanimine (polyPMI) using an imine metathesis reaction. We have demonstrated that this polymer can be used to stabilize silicon nanoparticles to produce a composite lithium-ion battery anode that is electrochemically stable for hundreds of lithiation and delithiation cycles with a Coulombic efficiency that is greater than 99.95% in a traditional carbonate liquid electrolyte.1 This novel polymeric coating passivates silicon nanoparticles by shielding them from direct electrolyte contact while maintaining effective ionic and electronic transport and also imbues the electrodes with excellent mechanical resilience to the volumetric changes experienced during cycling. We will cover the structure/property relationship of polyPMI within the context of the unique mechanical and electrochemical requirements of nanoparticle silicon anodes. We will also discuss the electrochemical behavior of this polymer and how it also offers new opportunities as an organic lithium-coordinating material that can be used to stabilize a variety of other battery electrodes. More broadly, we will posit that this solution-processed, ionically conductive, and electronically conductive polymer is applicable for a variety of energy storage and conversion technologies. Finally, this work will demonstrate how this novel polymer chemistry provides additional opportunities for tuning electrode architecture to target high areal capacity electrodes that enable high gravimetric and volumetric capacity full cells.
1. T. R. Martin et al., Adv. Energy Mater., 2203921 (2023).