bluuebunny/crossref_metadata_2025 huggingface dataset:
Lithiophilic Nanowire Architectures as Hosts for Lithium Metal Anodes
Authors: Abdul Ahad Syed , Bhattacharya Shayon , Ottaviani Michela , Ryan Kevin M , Kennedy Tadhg , Thompson Damien , Geaney Hugh
Published: February 2024

Lithium (Li) metal is considered the ‘holy grail’ of battery anodes and has attracted enormous interest due to its low density (0.59 g cm-3), high theoretical capacity (3860 mAh g-1) and lowest electrochemical potential (-3.07 V vs. standard hydrogen electrode - SHE) [1-2]. However, several issues during its cycling in a Li-metal battery (LMB) have hindered its commercialization. Some notable problems include the formation of an unstable solid electrolyte interphase (SEI), excessive dendrite growth and subsequent short-circuiting during the Li stripping/plating process [3-4].

In our poster presentation, we will detail the design of a hierarchical nanowire (NW) – Carbon paper (CP) host for dendrite-free and stable cycling in LMBs. These NWs were grown on high surface area carbon paper substrate via a modified Vapour-Liquid-Solid (VLS) approach. The lithiophilic NWs enabled quick Li infusion (< 10 sec) in the NW-CP substrate whereas no Li infusion was possible in lithiophobic bare CP substrate (without the presence of NWs). Additionally, the NW morphology helped in reducing the localized current density on the surface of the NW-CP host, thereby promoting uniform Li deposition during plating/stripping process. With careful design of the NW-CP host, symmetric cell performance with high current density (3 mA cm-2) and areal capacity (3 mAh cm-2) was achieved for up to 500 h while a typical Li metal anode failed within 200 h. High loading NMC811 and high specific capacity Sulfur (S) cathodes demonstrated superior performance using NW-CP host as compared to pristine Li anodes.

In addition, we will also present some new concepts of NW decorated lithiophilic interlayers, which can be integrated with pristine Li metal anodes for uniform Li deposition. These lithiophilic interlayers can promote ‘bottom-up’ Li infilling between the Li-interlayer interface such that dendrite formation near the separator and eventual short-circuit is avoided. Detailed electrochemical as well as density functional theory (DFT) analysis shedding light on the improved lithiophilic properties of NW use in stabilizing Li metal anodes will also be presented. Overall, our work is aimed to develop high energy density (ED) Li metal anodes to meet the rising ED demands of electric vehicle (EV) industry.

References

[1] Nat. Nanotechnol.
2017, 12, 194.

[2] Chem. Rev.
2017, 117, 10403.

[3] Chem. Soc. Rev.
2013, 42, 9011.

[4] Chem. Rev.
2004, 104, 4303.
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.
Shunt Current Analysis of Vanadium Redox Flow Battery System with Multi-Stack Connections
Authors: Zhao Xiaobo , Jung Seunghun
Published: February 2024

Vanadium redox flow battery (VRFB) systems with multiple stacks due to long lifetime, low self-discharge, and flexible design, are commonly used in large-scale electrical energy storage applications In a VRFB system, pumps deliver positive and negative electrolytes to each stack through a piping system including channels and manifolds. However, the electrolyte flowing between cells through channels and manifolds and the electrolyte flowing between stacks through pipes are electrically conductive. Shunt currents are generated due to the voltage difference between the cells and between the stacks, which reduce the energy efficiency of the battery system. In particular, under different load connections, the shunt currents of a multi-stack VRFB system have different distributions and cause different impairments to the system efficiency. Therefore, it is important to predict the shunt currents of the multi-stack system under different load connections before the actual construction of the system. In this paper, a multi-stack VRFB system with 120 cells was explored by circuit-based modeling to evaluate the shunt currents according to the stack configuration such as serial, parallel, and mixed connections.Then, the Coulomb efficiencies (CEs) were investigated with operating currents at 36 and 54A. The results show that shunt currents are generally more significant at the center cell of a stack than at other cells under these stack configurations and exhibit a positive correlation with the battery state of charge (SOC), i.e., larger shunt currents increase with SOC. In addition, the CEs of the system are higher at 54A compared to those at 36A due to smaller shunt current losses regardless of the stack configurations. Furthermore, regardless of the operating current levels, the multi-stack system connected by parallel loads achieves the highest CEs compared to the series and mixed connected systems due to the absence of shunt current losses in the piping system.

Figure 1
Bipolar Electrochemistry for Functionalization of 2D Materials
Authors: Bazylevska Anastasiia , Rodríguez González Miriam C. , De Feyter Steven
Published: February 2024

After the isolation of graphene monolayer graphene 2D materials have garnered great attention for their theoretically predicted exceptional properties. Covalent functionalization strategies are used to further finetune and improve these properties, which allow to integrate these materials into a wide range of applications. However, these strategies need highly reactive conditions, which do not guarantee a control over the degree and homogeneity of functionalization of the surface. Moreover, existing methods do not allow the functionalization of non-conductive surfaces and not much work has been done on 2D materials besides graphene. Additionally, there is a need in obtaining these 2D materials in a scalable fashion to be viable for industrial application. In this work we propose a scalable, low cost, facile method to achieve both exfoliation and functionalization in one-pot using bipolar electrochemistry for the production of 2D material in dispersions. Bipolar electrochemistry applies a high voltage to the electrolyte cell, and a gradient of the electric field occurs over the cell which induces the polarization of material placed between two electrodes. The polarization drives simultaneous reduction and oxidation reactions at the opposite poles of the placed material. This opens possibilities of functionalization of inert and semiconductor materials. The material is characterized with a range of techniques including Raman, AFM and TEM.

References

Line Koefoed, Kyoko Shimizu, Steen Uttrup Pedersen, Kim Daasbjerg, Alexander Kuhn and Dodzi Zigah, RSC Advances, 6 (2016), 3882–3887

Yong Wang, Carmen C. Mayorga-Martinez, Xinyi Chia, Zdeněk Sofer and Martin Pumera, Nanoscale, 10 (2018), 7298-7303

Line Koefoed, Emil Bjerglund Pedersen, Lena Thyssen, Jesper Vinther, Thomas Kristiansen, Steen U. Pedersen, and Kim Daasbjerg, Langmuir, 32(25), 6289–6296

Figure 1
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.
Stimuli-Responsive CeO2 Removal Via Surface Redox Modulation during Shallow Trench Isolation (STI) Post-Chemical Mechanical Planarization (p-CMP)
Authors: Cahue Tatiana R. , Gentile Ryan J. , Keleher Jason J.
Published: February 2024

As transistor miniaturization continues to extend Moore’s Law into the future of technology, the demand for high-efficiency device manufacturing processes has increased drastically in recent years. More specifically, a critical step in preparing integrated circuits (ICs) and logic devices is Chemical Mechanical Planarization (CMP), which relies on a delicate balance of chemical and mechanical parameters to achieve angstrom-level surface uniformity and ultimately allows for increased transistor packing density. A sub-area of CMP that has gained significant attention is Shallow Trench Isolation (STI), which involves the isolation of electrically active components by removing the bulk oxide (i.e., tetraethyl orthosilicate (TEOS)) overburden from the deposition process. During polishing, chemical slurries comprised of CeO2 nanoparticles, rate enhancers, selectivity and rheology modifiers, and pH adjusters are utilized to activate the oxide layer and consequently remove material. The STI removal mechanism, known as the chemical tooth model, involves the nucleophilic attack of CeO2 nanoparticles at surface defect states (i.e., oxygen vacancies (Ovacs)) and resultant dative Ce-O-Si bond formation, which makes the surface redox state of CeO2 (i.e., Ce3+/Ce4+) a key driver for oxide-nanoparticle interactions. It is well known that Ce3+ nanoparticles contain a higher concentration of Ovacs, which enhances the material removal rate (MRR). However, the hard adsorption properties of CeO2 have resulted in the demand for a more efficient post-CMP (p-CMP) cleaning process for TEOS that promotes increased CeO2 removal without inducing secondary defects (i.e., scratching, dishing, corrosion, etc.). Current industry-standard methods involve using a polyvinyl alcohol (PVA) brush to transport harsh chemistries to contaminated surfaces under high shear force (SF). Additionally, the use of megasonic energy is an emerging non-contact cleaning mode that relies on generating reactive oxygen species (ROS) (i.e., cavitations) to induce particle removal. Previous work has shown that supramolecular additives improve overall particle removal efficiency (PRE) when implemented in traditional PVA brush cleaning due to their ability to encapsulate and charge-flip CeO2 nanoparticles while reducing SF. As a result, this research investigates a combinatorial approach to PVA brush cleaning utilizing megasonic energy to release Fenton catalysts from polymer capsules, which aid in the production of ROS through H2O2 decomposition. Initial results have shown that, by increasing the concentration of ROS during cleaning, a Ce3+ à Ce4+ transition occurs on the surface of adsorbed CeO2, enhancing overall PRE.
RuNiOx Interface Promotes Hydrogen Production from Alkaline Seawater
Authors: Luo Hao , Guo Zheng Xiao
Published: February 2024

Hydrogen production from seawater is increasingly important as an alternative technic for realizing low-cost and green energy without exacerbating CO2 emissions due to the abundant seawater in nature. However, practical application is still hindered by the electrochemical catalyst’ poor stability under rigorous industry conditions. Herein, nanoplate ruthenium-nickel oxide (RuNiOx) supported on nickel foam is fabricated for hydrogen production from alkaline seawater with eminent stability. Mechanism study shows the real active center is the in-situ formed ruthenium cluster with the supported NiO. The interface of cluster Ru with NiO results in reduced water-dissociated energy for the Volmer step. This robust electrode exhibits an overpotential of 16mV at 10 mA cm-2 with a small Tafel slope of 21.3mVdec-1. It can be operated under a large current density at 1000 mA cm-2 over 350 hours in alkaline freshwater. When paired with oxygen-produced catalyst S-NiFeOOH, this electrode can work at an industrial current density of 500 mA cm-2 for 100 hours and even 1A cm-2 over 30 hours in alkaline seawater. At industrial temperature (65 ℃), 12 hours of operation can be achieved. This work paves a feasible pathway for hydrogen production from seawater industry applications.
Electrochemical Production of Methyltetrahydrofuran, a Biofuel for Diesel Engines
Authors: Stankovic Mia D. , Sperryn Jessica F. , Berlinguette Curtis P.
Published: February 2024

Methyltetrahydrofuran (MTHF) can be derived from non-edible biomass and used to replace diesel fuel. MTHF can be produced through the hydrogenation of furfural using hydrogen sourced from methane. Electrochemical hydrogenation (ECH) offers a method to source hydrogen from water, while bypassing the challenges associated with H2 handling and storage. Thus, if furfural were converted into MTHF through ECH, clean liquid fuels could be formed for internal combustion engines. The challenge is that ECH has not been proven to produce MTHF in meaningful yields due to solubility and thermodynamic constraints. We report here the successful electrochemically-driven hydrogenation of furfural to MTHF using a membrane reactor. This membrane reactor is able to produce MTHF production because the site of water electrolysis is separated from the site of hydrogenation so that hydrogenation can occur in organic media at high current densities. We show how the membrane reactor favors MTHF production at a selectivity of >75% at 200 mA/cm2, compared to conventional ECH using a single cell that operates at lower selectivities (<35%) and current densities (50 mA/cm2). We mapped out the reaction pathways to show that MTHF is produced from the deoxygenation of a furfuryl alcohol intermediate, a pathway that does not occur in single-cell ECH. This work shows the power of using the membrane reactor for producing liquid fuel alternative from a biomass-derived chemical, water, and electricity.
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
Enhanced Oxygen Evolution Reaction Activity of Fe-Doped Lithium Nickel-Based Metal Oxide through Modification of Nickel Oxidation State
Authors: Jung Young HAN , Tamboli Asiya Mohaseen , KIM Wan Sik , KIM Bonghyun , Sim Junseok , Kim Changhee
Published: February 2024

The oxygen evolution reaction (OER) involves the four-electron transfer process of water oxidation to produce oxygen gas and protons. However, this reaction is kinetically sluggish and requires high overpotential compared to hydrogen evolution reaction (HER). Herein, we have fabricated Fe-doped LiNiO2 using electrospray deposition (ESD) technique. With this technique, we can modify the electronic structure of LiNiO2 by controlling amounts of Fe, and the morphology can be controlled with various parameters such as applied voltage, spray rate, and substrate temperature. The synergistic effect of iron doping can modify the electronic structure of the surface Ni ions and increase oxidation state of Ni2+ to Ni3+. Through this oxidation state change, Ni becomes more electrophilic and then adsorbed oxygen in the M – O step, which is considered as rate-determining step in OER, easily reacts with OH ions. In electrochemical analysis, the optimized Fe-doped LiNiO2 showed improved OER performance compared to LiNiO2. The surface chemical compositions of the Fe-doped LiNiO2 electrode were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). From our result, we can improve OER performance and stability with simple control of ESD technique parameters and electronic structure modification by Fe doping.
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
Using an Electrochemical Deblocking Step in ASO Synthesis to Produce Quicker and Higher Yields of Oligonucleotides
Authors: Rockaitis Austin , Kissel Daniel
Published: February 2024

Machado Joseph Disease is an autosomal dominant genetic disease caused by excessive glutamine repeat in the Ataxin protein. To treat the repeating protein, oligonucleotides are synthesized that act as primers to create new strands of DNA or RNA to correct the genetic sequence causing the disease. The conventional synthesis method requires a five-step approach, using phosphoramidites anchored to solid supports. Deblocking is the first step of this cycle, where the phosphoramidite blocking agent is chemically removed. Traditionally, dichloroacetic acid in methanolic acid is used to remove the blocking group, N, N-Dimethyltryptamine, and replace it with a reactive alcohol group. The efficiency of the deblocking step can vary depending on a variety of factors including the amount of experience the experimenter has, the purity of the reagents, and the amount of time needed for the reaction. Using an electrochemical deblocking step, however, limits the number of factors by delivering the acid to a specific region on the phosphoramidite thereby directing nucleotide addition at a chosen site. Creating a more direct addition allows for more precise synthesis resulting in higher yields and more complex oligonucleotide chains. This work reports the synthesis and characterization of a novel ASO synthesized using an electrochemical deblocking step.
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).
(Invited) Impact of Binder Selection in Advanced Lithium Battery Electrode Fabrication and Performance
Authors: Dai Fang , Cai Mei
Published: February 2024

Polymer based binder plays an important role in electrode structures for varies energy storage systems such as battery and capacitor. In conventional wet coating process for battery electrode fabrication process, the polymer binders are mixed with the active material and conductive additives to form the slurry for the coating. The binders provide both physical and chemical supporting to the overall electrode structure, in addition to the basic “gluing” function. In recent years, a lot of aqueous soluble polymers were introduced in lithium-ion battery study working as alternative of traditional PVDF binder. The application of aqueous based polymer binder covers graphite, silicon, metal oxide, and even sulfur electrode fabrication. In this talk we will present some of our recent study on selected polymer binders in certain chemistry, such as Li-S system. We will reveal the difference in both physical and chemical properties of the selected binders, as well as the impact on the overall electrochemical performance. We will also discuss the binder selection and challenges from manufacturing point of view.
Development of Dual-Functional Polyamide Imidazole Binder for Silicon Anode Lithium-Ion Battery
Authors: Kim Junho , Park You Kyung , Choi Seong Hoon , Ko Da Young , Jung In Hwan , Kim Hansu
Published: February 2024

Silicon (Si) is one of the most promising anode materials in lithium-ion batteries (LIBs). However, Si undergoes a huge volume change during charging/discharging and induces intractable problems such as delamination, cracking of electrode, and unstable solid electrolyte interphase. Polymer binder is one of powerful strategies to prevent the problem. In this study, the novel polyamide imidazole (PAID) binder is synthesized and forms imide and imidazole intermediate phase (i-PAID) at electrode fabrication temperature. The i-PAID binder have strong interaction with Si particle and carbon black by ambidextrous binding effect. Introduction of amine and carboxylic acid in i-PAID binder enhances adhesion force of the Si particles. In addition, the extended polymer backbone of i-PAID improves not only inter-molecular interaction with carbon black by π-π stacking interaction but also sustains robust conduction pathway in Si anode. The Si anode with i-PAID binder confirmed outstanding mechanical durability of Si during charging/discharging through in-situ electrochemical dilatometer and ex-situ SEM observation. It exhibited higher reversible capacity and stable cycle performance for 200 cycles at 0.2C than the Si anode with commercial polyimide binder, respectively. Thus, the ambidextrous polymer binder would propose new molecular design concept for Si anode in LIBs.
Enhancing Performance of Anode-Free Li-Metal Batteries
Authors: Marrache Roy , Assa Tamir , Faktorovich Lina , Mukra Tzach , Shekhter Pini , Peled Emanuel
Published: February 2024

Because of their higher energy density, compared to lithium-ion batteries, rechargeable lithium-metal

batteries (LMB) have been considered one of the most attractive next-generation energy-storage

systems (ESS). A promising approach to improving LMB performance, that has gained interest in

recent years, is the use of anode-free lithium-metal batteries (AFLMB). Such battery configuration

enables elimination of the problem of using excessive amounts of lithium in LMBs, hence increasing

the specific energy of the battery. This work explores the beneficial effects of integrating metal-oxide

nanoparticles (MONPs) into the liquid electrolyte of AFLMB. It was found that the addition of low

concentrations of MONPs significantly improves coulombic efficiency (CE), capacity retention (CR)

and the Solid-Electrolyte-Interphase (SEI) properties. SEM images revealed a smoother lithium

morphology for MONPs cells and XPS analysis showed great differences in the SEI composition. The

resistance of the cell components, extracted via electrochemical impedance spectroscopy (EIS), has

been significantly lowered due to the addition of MONPs. The performance of the AFLMB, without

MONPs, was 97.1% CE and CR of 70% within 12 cycles, while cells with 0.5% SnO2 , 1% Al2O3 and

1% TiO2 was 99.1%, 98.8% and 99.4% CE, and CR of 70% within 39, 38 and 36 cycles, respectively.

Combinations of two MONPs resulted in 99.9% CE, which is among the highest found in the literature

for AFLMB.
Solution Processable Polyaniline with High Electrochemical Charge Capacity
Authors: Gettler Ryan , Kinlen Patrick , Young Matthias , Renfroe S. Emad , Xing Yangchuan
Published: February 2024

Polyaniline (PANI) is a charged polymer well-known for its high charge storage capacity and moderate electrical conductivity. PANI is often prepared by chemical or electro-polymerization, however, these polymerization methods limit options for substrate material, electrode/device geometry, and polymer morphology. To address these limitations, it is attractive to form PANI films by solution-casting. In this study, we examine the electrochemical properties of solution-cast PANI films formed from a commercially available PANI suspension containing excess dinonylnaphthalenesulfonic acid (DNNSA). Films prepared by solution casting of PANI-DNNSA have been previously characterized in terms of conductivity, morphology, and optical properties, however the electrochemical behavior of these films has been largely unexplored. Here, we present an electrochemical analysis of these solution-cast PANI films using quartz crystal microbalance, electrochemical impedance spectroscopy, and cyclic voltammetry. As cast, we find that the polymer exhibits limited electrochemical activity, but that postprocessing the material with electrolyte and crosslinking solutions increases the charge capacity up to 95 mAh/g – 86% of the charge capacity typically reported for electrodeposited PANI films. Ion-exchange processes, electrochemical capacitance, and energy storage capabilities of the chemically treated solution-cast films are assessed and compared to those of electro-deposited and chemically oxidized PANI. We demonstrate redox-active PANI films on both (a) conductive and insulating, and (b) planar and porous substrates. Finally, symmetric faradaic supercapacitor devices were constructed using spin-coated PANI electrodes in aqueous electrolyte, and the stability of these devices was examined by repeat galvanostatic charging/discharging at low current, achieving up to 88% capacity retention after 500 charge-discharge cycles.
(Keynote) Interplay of Aging Temperature and Thermophysical Properties of Lithium-Ion Battery Electrodes
Authors: Marconnet Amy , Herberger Sabrina , Paarmann Sabine , Seegert Philipp , Wetzel Thomas
Published: February 2024

While it is well known that the electrochemical performance of lithium-ion batteries degrades with repeated cycling, the impact of aging on thermal properties is less well understood. Degradation of thermal transport within the cell can lead to increased or even excessive temperatures that in turn lead to accelerated ageing or even thermal runaway. Thus, understanding how aging impacts thermal properties is critical to ensuring safe and reliable operation of batteries. In this presentation, we evaluate the evolution of the thermal diffusivity, heat capacity, and density of the electrodes of lithium-ion battery cells which were aged at different thermal conditions. From the measured properties, we estimate the thermal conductivity of the electrodes and the active materials in the electrodes as well. Overall, the transport properties approximately follow a trend with the time-averaged temperature during the aging process. The changes in the thermal properties are correlated with observations of changes to the microstructure of the electrodes during cycling. These results can impact the design of battery systems for improved performance and stability throughout their lifetime.