bluuebunny/crossref_metadata_2025_split huggingface dataset:
Tailored Electrolytes for New Redox-Active Polymers
Authors: Su Po-Hua , Asenbauer Jakob , Baumert Marcel , Le Victoria , Voll Dominik , Hansmann Max , Theato Patrick , Bresser Dominic 
Published: November 2022

Radical polymers are gaining increasing interest as active materials for batteries owing to their great potential for fast charging, and the fact that no critical elements are involved. PTMA [poly(2,2,6,6- tetramethylpiperidinyloxy-4-yl methacrylate)] is one of the best-investigated radical polymers for lithium batteries, providing high redox activity, fast kinetics and great reversibility during cycling.1 However, the electrochemically active nitroxyl radicals are embedded in a six-membered ring with four methyl groups attached to stabilize the radical, which limits its theoretical capacity due to the rather high molecular weight of the overall functional moiety. To increase the theoretical capacity, a decrease of the “unnecessary” mass is therefore desirable. Smaller redox-active molecules, however, commonly show a high solubility in liquid electrolytes, which prevents stable long-term cycling.
Herein, we present a new redox-active polymer based on low molecular weight amides, for which the solubility issue has been overcome by proper design. We show that the electrolyte composition (salt concentration and the choice of solvents as well as their ratio) plays a decisive role for (i) the redox behavior and kinetics (broad vs. sharp redox peaks and the redox peak separation), (ii) the eventual redox potential, which is greater than for PTMA, and (iii) the long-term stable cycling at high dis-/charge rates. As a result, the rational optimization of the electrolyte composition enables achieving excellent electrochemical performance, rendering this new class of polymers highly promising for high-performance rechargeable batteries. Finally, we unveil the underlying phenomena by means of complementary ex situ and in situ characterization techniques to provide an in-depth understanding and, thus, allow for the tailored design of suitable electrolyte compositions for this new class of redox-active polymers and, potentially, polymer electrode materials in general.
(1) Kim, J.-K.; Kim, Y.; Park, S.; Ko, H.; Kim, Y. Encapsulation of Organic Active Materials in Carbon Nanotubes for Application to High-Electrochemical-Performance Sodium Batteries. Energy Environ. Sci.
2016, 9 (4), 1264–1269. https://doi.org/10.1039/C5EE02806J.
Statistical Approach to Design Zn Particle Size, Shape, and Crystallinity for Alkaline Batteries
Authors: Lenhart Brian , Zuraw Michael , Mustain William Earl 
Published: November 2022

The modern alkaline primary battery is composed of a highly alkaline, gelled electrolyte-zinc powder anode dispersion (slurry), a cellulose-based separator, and an electrolytic manganese dioxide (EMD) cathode pellet – typically arranged in a cylindrical cell geometry. This battery system has its origins in the 1950s and thus has had decades to be researched and matured and it is known that the limiting performance of this battery system is concentrated at the slurried zinc anode. This had led many researchers to focus on the anode for improvement with most previous engineering efforts targeting enhanced performance, capacity, and stability of this material. Due to the various material fabrication processes involved with manufacturing industrial zinc powder, there exists an array of unique zinc particle size, shape, and crystallinity combinations that distinguish industrial zinc powders from one another. These industrial zinc powders are typically produced through trial-and-error processes using existing “rules of thumb”. Consequentially, it is possible that something has been missed and a data-driven approach could elucidate the optimum combination of zinc particle properties.
In this study, we investigate the effect of Zn particle size, shape, and degree of crystallinity on the achievable capacity and corrosion current. Various types of zinc powders were sieved into size fraction ranges and chemically and thermo-chemically treated to control their crystallinity. The procedure for producing zinc powders of various sizes, shapes, and crystallinities led to a 64-powder Zn matrix that was then electrochemically analyzed by linear sweep voltammetry to determine the corrosion current and galvanostatically discharged to determine the achievable capacity. These experiments were done in a newly-designed, custom-built electroanalytical cell that will be described in the talk. Following the data collection, a 4k factorial statistical analysis was performed. This analysis identified which of the controlling variables have a statistically significant influence on the achievable capacity and corrosion. The statistical model was also able to provide guidance regarding the preferred particle shape. This information can be used to develop actionable procedures for battery manufacturers to create cells that are more stable, longer lasting, and have higher energy densities.
Dynamic Impedance Spectroscopy of Lithium Plating from Next Generation Electrolytes
Authors: Sacci Robert L , Westover Andrew S , Yu Zhiao , Bao Zhenan 
Published: November 2022

The anode-free cells have emerged due to the need to maximize Li metal batteries' energy density. However, anode-free Li batteries suffer from short cycle life because of the lack of Li inventory at the anode. Freshly deposited Li metal anodes usually take hundreds of cycles to reach initial SEI stabilization optimum coulombic efficiency (CE) due to initial SEI stabilization and electrode activation. The anode-free cell design requires high Li metal CE over the whole cycling life, particularly during the initial activation cycles. A holistic approach to electrolyte design, mechanism understanding, and battery engineering is needed to fulfill these requirements. Here, we present a mechanistic study on lithium plating and stripping from next generation electrolytes.
We conducted dynamic impedance spectroscopy (dEIS) to probe the formation and evolution of the SEI during Li plating and stripping on copper current collectors. dEIS superimposes a multisine waveform atop the dc stimulus signal, as shown by the lightly shaded curves in Fig 1 (top left). We applied a sliding window FFT protocol that takes the complex ratio of the measured potential and current signals obtained from Fig 1 (top right) and transforms it into complex impedance. We will discuss two Li platting systems, Lipon (an amorphous ceramic) and a liquid electrolyte with stabilizing additives. We observed drastic changes in the cells' impedance during plating and stripping, Figure 1 (bottom plots). We will show how the passivation layer's impedance continues to evolve during Li cycling and accounts for a significant amount of the overall cell resistance.
The US Department of Energy’s Energy Efficiency and Renewable Energy Vehicles Technologies Office provided funding for this work under the US-German Cooperation on Energy Storage: Lithium-Solid-Electrolyte Interfaces program.

Figure 1
Quantification of Hydrogen Evolution on a Zinc Rotating Disk Electrode in Traditional Alkaline Electrolytes and Acetate-Based Water-in-Salt “Wise” Electrolytes
Authors: Dutta Debayon , Messinger Robert J. , Turney Damon E. , Banerjee Sanjoy , Lambert Timothy N. 
Published: November 2022

Rechargeable batteries as energy storage devices for the electric grid are advantageous to bridge the intermittency in the daily energy demand and production by renewable energy sources such as solar microgrids. Another important consideration to satiate this energy landscape is the need for inexpensive, safe, and non-toxic rechargeable battery technology and chemistry. Zinc aqueous (alkaline) batteries are one of the prime candidates that satisfies the aforementioned criterion and has thus warranted a lot of scientific and technological research for commercial applicability. There has been considerable work conducted by the researchers in this field to bolster the cycle life and active material utilization of zinc in alkaline systems. However, zinc is thermodynamically susceptible to hydrogen gas evolution in alkaline solutions as witnessed by its Pourbaix diagram. On a device level, this affects the columbic efficiency due to the deleterious side reaction, which in turn negatively impacts the energy density of the battery. Water-in-salt electrolytes (WiSE) are a recently developed class of electrolytes that directly address this shortcoming of dilute electrolytes due to the modified solvation structure of water which lowers the activity of free water molecules in solution.
In this work, we show a type of non-toxic and cheap acetate-based WiSE that has lower hydrogen gassing rates when compared to traditional alkaline potassium hydroxide-based electrolytes. Specifically, we quantify hydrogen gas evolution at the zinc electrode-electrolyte interface using the rotating disk electrode technique at different overpotentials to show the remarked improvement in gassing observed. At overpotentials of 100, 300 and 500 mV, 27 m (molal) potassium acetate is observed to have gassing rates of up to 16 times less than that of 25 weight percent potassium hydroxide. Using the Koutecky-Levich equation, mass-transfer and kinetic parameters for the hydrogen evolution reaction were also determined. The results establish the applicability of this class of WiSE in reducing gassing on zinc and thus, improving the overall efficiency of zinc-based aqueous batteries.
Probing Solvation Thermodynamics of Lithium Battery Electrolytes through Potentiometric Methods
Authors: Kim Sang Cheol , Cui Yi 
Published: November 2022

The electrolyte is a principal component of a lithium battery that impacts almost every facet of the battery’s performance. Solvation of lithium ions in electrolyte solution is key to understanding the electrolyte, but our understanding of solvation lags behind its significance. Particularly, estimating solvation free energy has been largely limited to computational simulations. Despite their versatility, simulations can be computationally expensive, and experimental methods to complement simulations are desired.
We have recently introduced a potentiometric technique to probe the relative solvation free energy of lithium ions in battery electrolytes. We devised an electrochemical cell composed of two half-cells, with symmetric electrodes but asymmetric electrolytes. Whereas the open circuit potential of a conventional lithium-ion battery measures the free energy differences of lithium ions in the two electrodes, our experimental setup measures the energy differences of the lithium ions in two different electrolytes. By measuring the cell potential with a reference electrolyte, we can quantitatively characterize lithium ion solvation energy of an electrolyte of interest. The effects of concentration, anion and solvent on solvation energy are explored and verified with simulations. Particularly, we establish a correlation between cell potential (Ecell) and cyclability of high-performance electrolytes for lithium metal anodes. We find that solvents with more negative cell potentials and positive solvation energies—those weakly binding to Li+—lead to improved cycling stability. Weaker solvents are conjectured to have more anion-rich solvation structures that lead to anion-derived solid-electrolyte interphases, a hypothesis supported by cryogenic electron microscopy. It reveals that weaker solvation is correlated to an inorganic anion-derived solid-electrolyte interphase that stabilizes cycling.
Electrodeposition of Three-Dimensional Au Nanowire Networks and Their Application As Catalysts for Methanol Electro-Oxidation
Authors: Li Mohan , Ulrich Nils , Schubert Ina , Trautmann Christina , Toimil Molares Maria Eugenia 
Published: November 2022

In this talk we will first present the synthesis of free-standing, stable gold nanowire network with controlled morphology and geometry by ion-track technology and electrodeposition. Etched ion-track membranes with interconnected nanochannels are produced by sequential GeV heavy ion irradiation of polymer foils from four directions, and subsequent etching and enlargment of the created ion-tracks. Au nanowire networks with three different nanowire diameters are synthesized by potentiostatic electrodeposition in the templates. Nanowire growth rate and homogeneity are tuned by varying the deposition potential. The electrochemical surface area was determined for each sample by CV analysis of surface oxide reduction reaction charge transfer. We will also discuss the catalytic performance of these Au nanowire networks towards methanol electro-oxidation, acting as an electrode in a half-cell setup. High current density and high catalytic activity were recorded. The Au nanowire networks provided up to 200 times higher peak current density than a flat Au electrode, along with excellent long term cyclability, which the current density drops only 5% over 200 CV cycles. SEM studies of the morphology and crystallinity of the nanowires before and after the methanol oxidation reaction will also be presented in the talk.
Figure 1. (a) SEM image of Au nanowire network, (b) Cyclic Voltammograms recorded for a of Au nanowire network in 0.1 M KOH with (solid line) and without (dash line) 1 M MeOH.

Figure 1
Electrochemical Synthesis of Ammonia from Nitrate on Preferentially Oriented Cu2 O
Authors: Anastasiadou Dimitra , Hensen Emiel J.M. , Costa Figueiredo Marta 
Published: November 2022

Electrochemistry-based processes to produce ammonia have recently gained widespread interest by the scientific community because they provide a way to reduce the high carbon emissions currently associated with ammonia production. Global NH3 demand is expected to rise since it is included in various energy scenarios as a possible green transportation fuel and storage medium of renewable electricity involving fuel cells.1 Several electrochemical and hybrid electrochemical processes with plasma integration are currently being investigated to produce NH3 via different nitrogen sources, such as N2, NO3
-/NO2
- or NO. The utilization of NO3
- from wastewater sources can be valuable for the environmental and health issues associated with NO3
- contamination. Additionally, NO3
- electroreduction in aqueous media is an attractive approach to investigate the catalysis due to its high solubility and the low dissociation energy needed to break the N=O bond. Cu and Cu-based materials have extensively been studied for NH3 production through NO3
- electroreduction. Earlier studies on Cu single crystals2 in alkaline media showed that Cu (100) performs better than Cu (111) in reducing the NO2
- intermediate to hydroxylamine, which is believed to be the precursor to NH3. On the contrary, recent density functional theory calculations3 showed that a Cu−Cu couple with 2.57 Å distance serves as a catalytic center, leading to the conclusion that Cu (111) is the most active surface termination. In this work, preferentially oriented Cu2O crystals with (111), (100), and (110) terminations were obtained via electrodeposition and evaluated for their performance in NO3
- electroreduction to NH3 (Figure 1). To understand which oxidation state of Cu represents the active phase, the samples were investigated by in-situ Raman spectroscopy. According to a recent study, the active phase was a combination of Cu and Cu+.4 Our results point to the immediate reduction of remaining Cu+ species during application of -0.3V vs. Ag/AgCl and formation of Cu(OH)2 at more negative potentials. The presence of Cu(OH)2 was also apparent from ex-situ XPS and UV-Vis analysis. Moreover, post-reaction XRD analysis showed a retainment of the crystal orientation on the reduced Cu surfaces. All the nanostructured catalysts were active for NO3
- reduction and produced NH3 with faradaic efficiencies above 40%. Cu2O (111) was the most efficient for NH3 synthesis reaching a faradaic efficiency of up to 99%.
1 D. Anastasiadou, Electrochem. Sci. Adv.,submitted.

2 E. Pérez-Gallent, Electrochim. Acta, 2017, 227, 77–84.
3 T. Hu, ACS Catal., 2021, 11, 14417–14427.
4 Y. Wang, Angew. Chemie Int. Ed., 2020, 59, 5350–5354.

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The Electrochemical Deposition of Pd and Cucl Films on Graphene
Authors: Drexler Matthew N , Alamgir Faisal M. 
Published: November 2022

Surface limited redox replacement (SLRR) is an electrochemical technique for depositing metal films monolayers in thickness, typically on other metals. As interest in graphene as a highly conductive, chemically resistant support for metal nanoparticles has risen, some have sought to apply this deposition technique to graphene as an electrochemical alternative to other chemical or vacuum-based deposition techniques. To better understand the nature of the interactions between the metal and graphene, our group has used this technique to deposit Pt on graphene to observe the structure of Pt and its epitaxy with the substrate. We have previously found that Pt prefers to bind to the bridge sites of graphene, preferring to form a simple-cubic-like structure and producing a slight lattice compression. We sought to expand on this study by observing the interactions of Pd with graphene.
Pd was deposited on graphene using Cu-mediated SLRR, however, most Cu-mediated SLRR is performed with CuSO4 or Cu(ClO4)2 dissolved in H2SO4 or HClO4. This does not necessarily produce a strong Cu underpotential deposition feature on graphene, so HCl was used as the electrolyte instead. This produced a substantially more pronounced underpotential deposition feature, but cyclic voltammograms in this solution do not appear to agree with typical Cu-S-Cl Pourbaix diagram.
This also resulted in two different types of structures, primarily Cu-containing films and primarily Pd-containing nanoparticles. The films were always found in the presence of the particles, but the particles did not always have accompanying films. A structural analysis of the particles determined that they preferred to interface with graphene along the (110) planes of Pd and have a slight elongation along the [001] direction of about 1.6% when oriented such that their columns were visible in the scanning transmission electron microscope. Based on an analysis of their orientation, this alignment and elongation appear to be the result of Pd minimizing its interfacial strain with graphene. A structural and compositional analysis of the films determined them to be CuCl, and they prefer to interface with graphene along their (111) plane, although the reason for this particular orientation is unclear as there is weaker evidence for a correlation between the alignment of the graphene and the films.
Characterization of Protective Coatings on Stainless Steel Bipolar Plates for PEM Electrolyzers
Authors: Leimbach Martin , Kurniawan Mario , Zimmermann Christoph Philipp , Höß Christian Elieser , Fritz Mathias , Bund Andreas 
Published: November 2022

Hydrogen production by electrolysis offers significant advantages over established and more common processes such as steam reforming with regard to CO2 emissions, in particular through the use of electrical energy from renewable sources and the establishment of a decentralized supply structure. The advantages of PEM (proton exchange membrane) electrolysis include high power density, scalability, and the high purity of the produced hydrogen. However, so far the manufacturing of the PEM electrolyzers is realized only on small scale, which makes the widespread use difficult and is a main cost driver for electrolyzer systems.
In the scope of the publically funded lead project H2Giga, a series of manufacturing processes are developed for industrial scale-up production of PEM electrolyzer components, in particular the bipolar plates (BPP) and the porous transport layers (PTL). Base materials like stainless steel are used that can be processed at a low cost but need protective coatings to withstand the highly corrosive conditions during electrolysis, especially at the anode side of each cell.
In our approach, these coatings are produced by electroplating, and their protective properties are investigated by electrochemical and surface characterization techniques. Precious metals (e.g. gold, platinum) are promising due their good stability at high anodic potentials and low pH values. However, nickel alloys, especially tin-nickel, could offer a cost-effective alternative. An improved stability of the tin-nickel alloy is observed above +1.5 V vs. NHE which can be attributed to the formation of an oxide layer. The coating systems showing the best results are investigated further in a multi-cell stack setup.
Electrodeposition of Ni-Fe Alloy in Presence of Complexing Agent
Authors: Park Jung-Joon , Seo Jinmyeong , Yoon Sanghwa , Yoo Bongyoung 
Published: November 2022

The nickel-iron alloys have been widely used for versatile soft magnetic applications and electro-magnetic applications due to their magnetic properties for a long time. Also, it has been discovered that Ni-Fe alloy near 36 wt% Ni shows almost zero thermal expansion composition(CTE) in a wide temperature range (~150 ℃). The phenomenon showing low CTE in a specific composition is called the Invar effect. Due to the Invar effect, Invar alloys are used for temperature-sensitive applications such as oscillators and fiber-optic package parts. Invar alloy films are used for fine metal masks, an essential part of OLED fabrication. The invar film currently in use is fabricated using the pyrometallurgy method, more than 20um thick. However, miniaturization and high performance of the products require the thinner thickness of the Invar film, around 10um thick which shows the need for a bottom-up fabrication process of invar film. There are various methodologies to fabricate thin films, such as thermal evaporation, sputtering, CVD, and electrodeposition. Most fabricating processes are the vacuum process, a high-cost and non-continuous process. On the other hand, electrodeposition is a non-vacuum process, relatively low-cost, large-scale, and continuous process.
Despite these advantages, there are some obstacles to gaining the Invar thin film by electrodeposition, such as anomalous deposition, composition uniformity, and higher CTE of electrodeposited Invar film. There are researches[1-3] about electrodeposited Ni-Fe thin films in the aspect of CTE, magnetic properties, crystal structures, etc. However, very few researchers have seen the effect of complexing agents other than specific complexing agents such as boric acid and ascorbic acid. In addition, Ni-Fe electrodeposition shows very different results depending on temperature and agitation, but no research confirms the effect on various complexing agents under the same condition.
In this study, we synthesized Ni-Fe alloy thin film by electrodeposition in the presence of various complexing agents with different functional groups (amine, carboxyl, alcohol, etc.) such as glycolic acid, malonic acid, ethylenediamine, etc. on 20um stainless 304 foil substrates. The electrodeposition was conducted under the aqueous acidic bath(pH 2) at 55℃. Electrochemical studies were conducted to set appropriate potential and current density for electrodeposition. The thin film was characterized by SEM, EDS, XRD, and copper strip tests to observe the difference in composition, surface morphology, phase, and internal stress.