bluuebunny/crossref_metadata_2025_split huggingface dataset:
Liquid Structure and Anti-Corrosion Effect of Super-Concentrated Electrolyte Solution
Authors: Watanabe Hikari , Yoshida Yurina , Shitanda Isao , Itagaki Masayuki 
Published: February 2024

For realizing sustainable world, Lithium-ion batteries are required to have higher energy density. Aluminum metal have been dominantly used as a current collector of positive electrode. A mixture of ethylene carbonate (EC) and dimethyl carbonate (DMC) containing 1 mol dm-3 Lithium hexafluorophosphate (LiPF6) has been used as an electrolyte solution. Aluminum forms thin passivation layer on its surface, preventing the corrosion. However, aluminum corrosion may occur due to this electrolyte solution under high voltage condition. Recently, super-concentrated electrolyte solution (SCES) [1], which consists of only two or three times as much solvent as lithium salt, has been attracting attention as a new electrolyte solution of high-voltage lithium-ion battery. Motsumoto et al. proposed that aluminum corrosion was remarkably suppressed in lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)-based SCES [2]. To clarify the corrosion-inhibiting factor of SCES, we investigated aluminum corrosion in the several lithium salts based SCESs [3]. And we found that lithium perchlorate (LiClO4)-based SCES could suppress corrosion of Aluminum current collector. Liquid structure of the SCES may plays an important role in corrosion suppression. In the present work, we demonstrated Raman spectroscopy and Quantum chemical calculations to reveal the liquid structure of the LiClO4-based SCES.
The LiClO4 based SCES was prepared by dissolving LiClO4 into DMC as the molar ratio of 1 : 2. For comparison, DMC solution containing 1 mol dm-3 LiClO4 and neat DMC was also prepared. Raman spectroscopic experiments were conducted using Laser Raman spectrophotometer (NRS-5100, JASCO) installed a laser at 532 nm. Quantum calculations were performed using the Gaussion 9 program suite (Gaussian, USA). Geometry optimization were conducted at the B3LYP/6-311+G(d,p) level. An intensive peak is observed at approximately 915 cm-1 for neat DMC. When a small amount of LiClO4 is added to DMC (corresponding to 1 mol dm-3 LiClO4 solution), new peak is observed at approximately 932 cm-1. This peak can be assigned to ClO4
-
anion. A new peak appears at approximately 950 cm-1 with increasing LiClO4 (corresponding to the SCES). According to the Quantum calculations, the new peak is assigned to aggregate in which the ClO4
- cross-links Li+. In addition, HOMO energy of a contact ion pair (CIP), in which ClO4
- coordinates to Li+, is lower than that of free ClO4
- anion. The oxidative stability of ClO4
- increases by forming CIP and aggregate. The decomposition products of ClO4
- may affect the Aluminum corrosion. The high oxidative stability of LiClO4-based SCES may prevent the Aluminum corrosion.
References
[1] J. Wang, Y. Yamada, K. Sodeyama, C. Chiang, Y. Tateyama, and A. Yamada, Nat. Commun., 7, 1-9, (2016).
[2] K. Matsumoto, K. Inoue, K. Nakahara, R. Yuge, T. Noguchi, and K. Utsugi, J. Power Sources, 231, 234-238 (2013)．
[3] H. Watanabe, Y. Yoshida, I. Shitanda, M. Itagaki, 242nd ECS Meeting, C04-0785
Operando Neutron Diffraction Analysis of Commercial Positive Electrodes of Lead Batteries
Authors: Hussey Daniel Seth , Rodriguez-Gomez Miguel , Larrea Arbaizar Angel , Campo Javier , Orera Alodia , de la Fuente Fernando , Valenciano Jesus , Fricke Holger , Chen Yan , Yu Dunji , An Ke 
Published: February 2024

We have analyzed by operando neutron diffraction the charge/discharge crystallographic transformation processes inside the positive active mass (PAM) of industrial lead batteries, getting information onthe spatial distribution of the phases. Our study was focused on the positive electrode because it is there where the main limitations to the charge/discharge efficiency are originated. The experiments were carried out in the VULCAN instrument at the Spallation Neutron Source of the Oak Ridge National Laboratory (Tennessee, USA) using the volume gauge technique. VULCAN is a high brightness time-of-flight diffractometer which provides fast volumetric mapping and, therefore, the possibility to study kinetic behaviors. Accordingly, both static and dynamic mapping experiments were performed during charge-discharge cycles, comparing fresh and cycled cells. The diffractograms obtained were analyzed using VDRIVE and GSAS software, together with dedicated Python scripts. In addition to compositional maps (Figure 1), information on lattice parameters, crystallinity, stoichiometry and hydration was also obtained as a function of the state of charge. Local inhomogeneities and differences in the behavior between fresh and cycled cells were observed. Moreover, we have used the Pb signal from the positive grid as internal calibrating element to obtain the absolute molar concentration of the component phases, comparing the PbSO4 PbO2 transformation with the effective charge driven by the cell during charge and discharge processes. The b-PbO2 mass utilization during the C5 100% to 20% discharge was about 0.3. In the same way, the charge factor was estimated to about 70%, from the start of charging until the PbO2 concentration reaches a near flat regime, and about 5% after reaching the flat regime. Giving for the full charging cycle a value about 50%.
As far as we know, this is the first time that diffraction information has been obtained from inside commercial thick electrodes (3.4 mm in thickness) during real operation conditions, mapping the PbO2 and PbSO4 evolution in a 2.24 cm x 7.2 cm region of the positive electrode.

Figure 1
Effect of Cu Pad Geometry and Dishing in Cu/Sicn Hybrid Bonding Process: A Finite Element Analysis Study
Authors: PARK So-Yeon , Kim Cha-Hee , Oh Gwang-Sik , Yun Young Su , Kang Jiho , Kim Sarah Eunkyung , Lee Won-Jun 
Published: February 2024

The Cu/dielectric hybrid bonding is a face-to-face wafer bonding technology that utilizes the thermal expansion of the Cu pad embedded in dielectrics. It is receiving significant attention due to the advantage of achieving high interconnect density through submicron-level fine-pitch bonding. The finite element method (FEM) is beneficial for hybrid bonding research because it provides insight on the bonding mechanism by simulating the expansion of the Cu pad with increasing temperature. The effects of pad shape and dishing by chemical-mechanical polishing (CMP) were studied by FEM for fixed dimensions of Cu pads, 4 or 10 μm in size and 0.5 μm in thickness [1] [2]. However, studies on the hybrid bonding process for Cu pads with finer dimensions and various geometries using FEM analysis are currently lacking.
In this study, we simulated the Cu/SiCN hybrid bonding process using ANSYS to investigate the effects of Cu pad geometry and Cu dishing by CMP. The diameter and thickness of the circular Cu pad were ranging from 0.1 to 1.5 μm and 0.15 to 0.45 μm. The Cu dishing depth was varied between 2 to 5 nm. For bonding process, at first the dielectrics of the two wafers were in contact with each other at room temperature. Then, the temperature was raised to the annealing temperature to simulate the Cu-to-Cu bonding process. At different annealing temperature, the bonding area was estimated with varying diameter, thickness, and dishing depth of the Cu pad. The Cu-to-Cu bonding area was mapped according to the Cu pad geometry, and the geometry of the Cu pad suitable for hybrid bonding was proposed. The protrusion of the Cu pad caused by the thermal expansion was also investigated for a single wafer to discuss the effect of the Cu pad dimension on the bonding area.

Acknowledgments This work was supported by SK hynix Inc.

References [1] Y. Beiliard et al., International Journal of Solids and Structures 117, 2017, pp.208 [2] C. Sart et al., 6th Electronic System-Integration Technology Conference (ESTC), 2016, pp. 1
(Invited) In-Operando ftir Study on the Redox Behavior of Sulfurized Polymers As Cathode Material for Li-S Batteries
Authors: Pereira Rhyz , Rafie Ayda , Fafarman Aaron , Kalra Vibha 
Published: February 2024

Sulfurized polymers are an attractive cathode active material, promising to overcome the intransigent polysulfide shuttle effect sulfur cathodes face via the anchoring of sulfur by a carbon-sulfur (C-S) bond. Both sulfur-diisopropenylbenzene copolymers (SDIB) and sulfurized polyacrylonitrile (SPAN) contain C-S bonds which should function in this way, however, their performance in ether electrolytes still exhibit capacity fade associated with the polysulfide shuttle. We investigate this anchoring effect using in-operando ATR-FTIR spectroscopy to develop a molecular level understanding of the polysulfide speciation reaction in sulfurized polymers and cathode level molecular changes. We find that in SDIB copolymers with sulfur wt % of 80 and 30 wt %, the C–S bond is not active in the voltage window of Li–S batteries (1.8-2.6V vs Li/Li+).
In SPAN, however, we found that the C-S bond is active in the typical voltage window (1-3V vs Li/Li+) contributing to the evolution of polysulfide species in electrolyte with low concentrations of lithium nitrate (LiNO3), however this effect is mitigated when higher concentrations of LiNO3 are used. We attributed the mitigation of the polysulfide shuttle to the formation of a cathode electrolyte interface (CEI), composed of lithium fluoride, established via ex-situ XPS studies on cycled cathodes. Additionally, we observed the reversible behavior of the C-S bond in IR at ~680 cm-1 in electrolytes with high concentration of LiNO3, as opposed to the irreversible behavior of the bond in electrolyte with low concentrations of LiNO3. Moreover, we observed the lithiation of the cyclized PAN backbone, identified by the elimination of the aromatic region of the IR spectrum after the first cycle.
Designing a Stable and Electrically Conductive Colloidal Suspension for Improved Flow Electrode Capacitive Deionization
Authors: Overland Alexandra E. L. , Ceron Maira Raquel , Hawks Steven A. 
Published: February 2024

With increasing effects from major droughts and water shortages, water desalination has garnered significant technological interest. Like many technologies, desalination suffers from high energy consumption, capital cost, process inefficiencies, and material degradation. Flow electrode capacitive deionization (FCDI) is a relatively new water desalination technology that combines aspects of electrodialysis and capacitive deionization to deliver a device which can achieve >90% water recovery at high productivity and thermodynamic efficiency. A fundamental challenge in FCDI, though, is engineering an electrically conductive slurry with excellent colloidal stability. Here, we explore the tradeoff between electrical conductivity and sedimentation rate using commercially available surfactants. We find that the optimal surfactant is non-intuitive and strongly depends on the type of carbon used in the slurry (e.g., activated carbon, carbon black, etc.).
This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344. Funding was provided by Lawrence Livermore National Laboratory Directed Research and Development (LDRD) Grant #22-DR-011. IM release number: LLNL-ABS-846651.
Comparing the Evolution of Lithium-Ion Cells across Energy, Power, Lifetime, and Temperature with the Enpolite Plot
Authors: Dechent Philipp , Jöst Dominik , Barbers Elias 
Published: February 2024

In the field of solar technologies, NREL has tracked the evolution of various technologies on the Best Research Cell Efficiency Chart for decades. This allows for a "sanity check" of a new technology, as there is a clear guideline for the entire solar field when a new technology has a significant advantage, even if it is small. In the battery field, however, many "wonder batteries" are presented that focus on only one indicator of battery performance, such as fast charging capability, while neglecting others such as energy density, cycle life, or operating temperature. This makes it difficult for even experts to evaluate new technologies.
On the other hand, with new efforts by the battery community to create an open and shared battery data ecosystem, a whole new set of data can be leveraged to create better and more holistic comparisons of new technologies to the state of the art. In addition to the previous publication of the ENPOLITE plot (doi.org/10.1021/acsenergylett.1c00743) and on the website https://enpolite.org/, in this paper we show our extension of the work on the plot to include a time scale.
The ENPOLITE plot is a highly informative tool for comparing the evolution of battery technology. At a glance, it provides crucial details such as capacity, cell format, cell chemistry, aging test duration, measurement temperature, specific power, energy density and achieved lifetime for each cell. In addition, the battery life coefficient derived from this plot allows comparison of lithium-ion batteries of different weights or volumes, capacities and cell chemistries.
The ENPOLITE Plot combines multiple parameters to facilitate a thorough comparison of various battery degradations, making it an incredibly useful tool for battery researchers and developers. It not only displays cell-specific parameters during cycling, but also includes information on specific stored energy and storage temperature in a calendar format. This comprehensive approach allows researchers to identify trends and patterns in battery performance, helping to develop more efficient and durable battery technology.
We hope to provide the battery community with a better tool for evaluating and ranking new technologies and improvements to existing battery types.

Figure 1
Silver-Alloys Electrodeposition for Electrical Conductivities
Authors: Orecchioni Quentin , Gigandet Marie-Pierre , Tardelli Joffrey , Hihn Jean-Yves 
Published: February 2024

The needs of the ecological transition are based on a larger use of electricity in several processes and access to new resources in large quantities such as hydrogen. The production of the latest by electrolysis as well as the electrification of the means of land transport and the anticipation of the needs of the aeronautics relies on higher capacities in current transmission. The specifications of the connectors and power transmission devices are increasingly stringent, requiring high-quality coatings when intended for contact current transmission. Silver and silver alloys appears to be an excellent choice for such application [1].
The standard electrochemical potential of silver being among the highest, the stability range of its oxides, in aqueous solution, is all the more reduced. In order to maintain these oxidized forms in solution and thus be able to reduce them to the cathode, formulations mixing complex, pH buffer system and other additives have been developed. The electroplating of hard silver in cyanide environments remains the most widely used industrial process, but the specifications can only be obtained by the use of chemical species whose mechanism of action is often poorly known. Moreover, nature and concentrations of additives used in the bath have a direct impact on the coatings properties. An alternative exists in the complexation of other metals with silver, to form an alloy with properties which depends strongly on the electrolysis parameters. To work properly, the working potential must be shifted from the thermodynamic equilibrium [2]. The present study is part of the SILAHPERF project, led by IRT-M2P and UTINAM Institute, which try to investigate the codeposition mechanism of various silver-based alloys of interest with a particular focus on silver-tungsten while seeking for environmental-friendly solution, focused on electrolysis parameters. Indeed, an alternative to cyanides as complexing agent is expected, face to the raising number of regulations. Therefore, a large number of complexing agent are evaluated, with their electrochemical behavior in i=f(E) curves, and with the deposition yield as well as the alloying element content as a function of the deposition potential. As an example for silver-tungsten alloys, complexing agents may be a combination of a carboxylic acid and an amino compound. The most popular couple is the citrate-thiourea system, however tartrate, oxalate, ammonia and urea are also good candidates. Finally, coating properties are evaluated by several technics (SEM – XRD, GDOES ...)
[1] M. Myers, ‘Overview of the Use of Silver in Connector Applications (503-1016), p. 14.
[2] A. Kola, X. Geng, and E. J. Podlaha, ‘Ag–W electrodeposits with high W content from thiourea–citrate electrolytes’, Journal of Electroanalytical Chemistry, vol. 761, pp. 125–130, Jan. 2016, doi: 10.1016/j.jelechem.2015.12.002.
Cu Foil Modification By Ag Inkjet Printing for Improved Li Plating in Anode-Free Li Batteries
Authors: Gibertini Eugenio , Mirbagheri Seyedalireza , Magagnin Luca 
Published: February 2024

The rush in the development of new generation of lithium-ion batteries (LIB) is focused on enhancing the specific energy of batteries by employing innovative materials and manufacturing techniques. Anode-free lithium metal batteries (AFLBs) are an emerging technology that can almost double the specific energy of LIBs by eliminating the conventional graphite negative electrode or excess lithium metal 1. However, AFLBs are well-known to suffer of fast capacity decay due to the poor lithium plating and stripping efficiency process associated to the typical porous growth of Li during charge 2. Tuning the interfacial electrochemistry was widely demonstrated to be one the most performing key to enable efficient and smooth Li deposition. In this regards, functional coatings of metals as Sn, Al, Zn and Ag have been widely demonstrated to dramatically improve the quality of Li plating process respect to the neat Cu foil substrate, by forming lithium-rich alloys that provide minimum Li nucleation overpotentials 3. Inkjet printing (IJP) could be a viable technique for electrode fabrication in LIBs manufacturing, being a quick, easy and scalable technology able to deposit both thin film and patterned structures 4. However, very poor attention has been paid so far to the potentiality of IJP for Cu modification for improved Li plating in AFLBs.
In this work, we employed a Fujifilm Dimatix inkjet printer to achieve “lithiophilic” coatings of Ag nanoparticles deposited on a Cu foil. In particular, potenziodynamic and galvanostatic electrochemical test were employed to investigate the effect of the Ag printed structures on the Li nucleation overpotential. Ex-situ morphological analysis by electron scanning microscopy (SEM) were usefully employed to investigate the surface evolution of the printed electrodes during lithium alloying and plating. In particular, the effect pf patterned Ag structured rather than fully coated Cu was investigated, revealing that patterning can provide more mechanically robust electrode and efficient catalytic sites for Li electrodeposition respect to fully coated inkjet printed electrodes.

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Preparation and Characterization of Tin-Nickel Coatings for Corrosion Protection of PEM Electrolyzer Components
Authors: Leimbach Martin , Kurniawan Mario , Aziz Carlos , Hoess Christian Elieser , Fritz Mathias , Bund Andreas 
Published: February 2024

Hydrogen production by electrolysis offers significant advantages over established and more common processes such as steam reforming with regard to carbon dioxide 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 PEM electrolyzers is time consuming, which makes the widespread use difficult and is a significant cost driver for this technology.
In the framework of the publically funded flagship 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.
A novel approach is focusing on nickel-based alloy coatings, in particular tin-nickel, which emerged as a promising alternative to precious metal coatings. These alloys show a wide stability range under strong anodic polarization in an acidic electrolyte due to the formation of a passive layer. However, the long-term stability does not yet meet the industrial requirements in preliminary tests. A post-treatment of the coating can improve the stability by the formation of a homogenous oxide film with several tens of nanometers in thickness. Physical, chemical and electrochemical methods for post-treatment were compared in terms of oxide morphology and corrosion behavior under anodic polarization. Eventually, both high corrosion resistance and low contact resistance have to be ensured for the application in PEM electrolyzers.
Electrochemical Strategies to Control Dendritic Growth in Sodium-Metal Batteries
Authors: Hosseinzadegan Meghdad , Nyholm Leif , Hernández Guiomar , Rehnlund David 
Published: February 2024

Sustainable development can be pursued through electrification in all sectors, and energy storage devices -mainly batteries- play a crucial role in this process. This leads to an ever-increasing demand for rechargeable batteries. However, the current generation of the rechargeable batteries, namely lithium-ion batteries, is produced using elements such as Li, Ni, and Co which have limited resources. Sodium-ion batteries (SIBs) on the other hand are considered as a good alternative due to the abundance of Na resources and fundamental similarities of Na and Li. While the cathode material for SIBs has reached a commercial level of reliability, the identification of a high energy anode material still remains a challenge. Although Na metal as an anode material offers high energy density, the main issue is that Na metal has a tendency for dendritic growth during electrodeposition.
In this work, different electrochemical strategies are used to mitigate dendritic Na growth. High overpotential nucleation pulses during stripping and/or plating steps are applied in order to induce two-dimensional growth. The impact of these strategies is studied using three-electrode symmetrical cells with Na metal as the working, counter, and reference electrodes, in an electrolyte composed of NaPF6 in EC/PC with FEC as an additive. Chronopotentiograms recorded during extended cycling (with and without Na pre-nucleation) are examined with special attention being paid to the overpotentials occurring on each cycle. Ex-situ SEM images are used to relate the different potential profiles during extended galvanostatic cycling to the different surface morphologies.
The results show that a combination of oxidative (stripping) and reductive (plating) pulses has an obvious effect on inhibiting dendritic growth during electrodeposition of Na metal. The results encourage the deployment of electrochemical strategies to prevent dendritic growth in Na metal anodes and paves the way for experiments with new electrolyte compositions to further help overcoming the challenges associated with Na deposition.