bluuebunny/crossref_metadata_2025 huggingface dataset:
The Effect of Cu and Zn Addition on the Intergranular Corrosion Resistance of Al-Mg-Si Alloy
Authors: Inagaki Mutsuki , Muto Izumi , Nishimoto Masashi , Minoda Tadashi , Takaya Mai , Kyo Yoshihiko , Sugawara Yu
Published: February 2024

Aluminum alloys are widely used for automobile and aircraft industries because of their good strength-to-weight ratio. In general, Cu improves the strength of Al alloys but reduces localized corrosion resistance. For Al-Mg-Si alloys, it has been reported that Cu decreases intergranular corrosion resistance. In this study, the effect of Cu and Zn on intergranular corrosion resistance was analyzed by electrochemical measurements.

As specimens, Cu-free alloy, Cu-added alloy, and Cu- and Zn-added alloy were prepared based on AA6061 composition. The extruded specimens were subjected to T6 heat treatment. Intermetallic compounds were characterized by SEM-EDS and TEM. Open-circuit potentials (OCPs) was measured in 0.1 M NaCl (pH 6.0). To assess the distribution density of the initiation sites of localized corrosion, the size of electrode area was 100 mm2, 9 mm2, or 1 mm2. In the electrochemical measurements, Ag/AgCl (3.33 M KCl) was used as the reference electrode.

At the beginning of immersion, OCP was −1.2 V (vs. SHE) for all specimens, and OCP increased with time. After 4000 s, the OCP of Cu-free alloy became −0.5 V, the OCPs of Cu-added alloy and Cu- and Zn-added alloy became −0.4 V. After 3 h immersion, intergranular corrosion was generated on Cu-added alloy and Cu- and Zn-added alloy. In contrast, no intergranular corrosion was observed on Cu-free alloy. Based on intergranular corrosion length, it was shown that intergranular corrosion resistance of Cu- and Zn-added alloy is low compared with the others. This result suggested that Zn promotes the growth of intergranular corrosion. Moreover, the number of intergranular corrosion damages was assessed and found to be less on Cu- and Zn-added alloy than on Cu-added alloy. This result suggested that Zn decrease the number of initiation sites of intergranular corrosion. Additionally, 3-h immersion of Cu-added alloy and Cu- and Zn-added alloy was conducted with the electrode area of 9 mm2 and 1 mm2. For both alloys, intergranular corrosion occurred at 10 sites in 100 mm2 and 1 site in 9 mm2. And no intergranular corrosion occurred in the case of 1 mm2 electrode area. The distribution density of the initiation sites for intergranular corrosion on Cu-added alloy and Cu- and Zn-added alloy was estimated to be approximately 1 site per 9 mm2.
Development of Hydrophilic Oxide/Polymer Composite Membranes for Polymer Electrolyte Fuel Cells Operating at Wide Temperature Range
Authors: Ohno Ryuji , Tano Tetsuro , Kakinuma Katsuyoshi
Published: February 2024

Toward the wide-spread use of heavy-duty vehicles (HDVs) operated by polymer electrolyte fuel cells (PEFCs) should approach the higher temperature around 120oC besides normal temperature (60-80oC). Commercial perfluorosulfonic acid-based electrolyte (PFSA, e.g. NafionⓇ) shows better proton conductivity with chemical stability in wide temperatures range, though decreases under low back pressure at 100~120 oC. In order to improve the proton conductivity at the higher temperature range, composite membrane of NafionⓇ with a hydrophilic filler of Ta doped TiO2 (Ta-TiO2) was synthesized. The Ta-TiO2 nanoparticles fillers with fused-aggregate network microstructure were synthesized by the flame method, and were crushed by wet mill(Star Burst, :Sugino Machine Limited CO.). The fillers were mixed with NafionⓇsolution (20 wt.%：D2020 Chemours Co.) by use of a rotary ultrasonic dispersing processor (500 rpm, 60 min. PR-1 :Thnky Co.), a planetary ball mill (500 rpm、30 min.：PULVERISETTE 6：FRITSCH Co.), and a defoaming processor (500 rpm、5 min.：HM-400W: Kyouritu Seiki). The dispersion solution was coated in hot air by use of a die coating system (die coater: Taku-Dai Mini-50: Daimon Co., Ltd.), and were hot-pressed (140 ℃ 3 min. TCMD-2.5:TOHO KOGYO co.) to form composite membranes (9 cm×9 cm ×25 µmt).

The cross-sectional backscattered electron image BSE) of the composite membrane observed by scanning electron microscope (SEM, acceleration voltage 2 kV, SU9000: Hitachi High-Tech Co.) and transmission electron microscope (TEM, H-9500: Hitachi High-Tech Co.). The proton conductivity of the composite membrane was measured by the AC four-probe method. The current-voltage (IV) polarization curves of Single cells using the prepared composite membrane (membrane thickness: 25 µm) were measured at 80 ℃ 100% RH and 120 ℃ 20% RH, back pressure 50 kPaG.

The obtained composite membranes were well flexibility with softness. The BSE images indicated that the high contrast images of Ta-TiO2 parties were uniformly dispersed in composite membrane. The higher magnified of the cross-sectional TEM images also showed that the hydrophilic surface of Ta-TiO2 adhered to the Nafion® without any air pores. The proton conductivity of the composite membrane at 80% RH increased with increasing Ta-TiO2 content and showed maximum value of 0.13 S cm-1at 3 wt%, and then decreased. The maximum proton conductivity was 1.3 times higher than that of Nafion®. The IV performance of the single cell using composite membrane kept same performance to that using Nafion® membrane at 80 oC 100% RH, and then improved at 120 oC 20% RH. The water content at 120 oC 20% RH kept higher value by the effect of hydrophilicity of the Ta-TiO2, which would be one of the reasons to enhance the cell performance at 120 oC 20% RH.

Figure 1
Deuterium Enrichment by PEM Water Electrolysis with Electrolyte Circulation
Authors: Sato Ibuki , Matsushima Hisayoshi , Ueda Mikito
Published: February 2024

Nuclear fusion is attracting attention as a new energy supply method. Nuclear fusion requires high purity deuterium (D) as fuel, but it is difficult to separate and enrich the isotopes because they have very similar chemical properties. In polymer electrolyte membrane water electrolysis (PEMWE), protium (H) is easily generated as hydrogen gas at the cathode electrode, while D can be concentrated in the electrolyte [1]. In this study for pursing high D enrichment process, the electrolyte circulation was employed and the relationship between the consumption ratio and D concentration was investigated.

The initial D concentrations in the electrolyte were 10, 30, and 50 at%. The electrolyte was supplied to the cathode. IrO2 was used as the anode catalyst and Pt/C as the cathode one. Experiments were conducted at atmospheric pressure and room temperature. The electrolysis was conducted at constant current. Hydrogen gas produced by electrolysis was analyzed by a quadrupole mass spectrometer (Q-Mass) to determine the ratio of H2, HD, and D2. The drain from the cathode was returned to the electrolyte reservoir. The electrolyte was analyzed by Fourier transform infrared spectrophotometer (FT-IR) to determine the ratio of H2O, HDO, and D2O.

The D concentrations, CD
, in the solution relative to the consumption ratio of the electrolyte, R, were shown in Fig. 1. The experimental results showed that CD
increased exponentially with R, confirming D enrichment in the electrolyte. Figure 2 shows the variation of the separation factor, α, in the gases as a function of R. α is the [H]/[D] ratio in the evolved gas divided by the [H]/[D] ratio in the liquid. H was concentrated in the gas. While about 90% of the electrolyte was consumed, α remained constant value (α ≈ 4), but as the electrolyte was further consumed, α dropped to about 3.

References

[1] K. Harada et al., Int. J. Hydrog. Energy, 45, 31389 (2020).

Figure 1
Micro-Regulate Ionomer Distribution to Increase Pt Utilization for PEMFC
Authors: Wen Zengyin , Fan Jiantao , Li Hui
Published: February 2024

In the past decade, numerous Pt-based oxygen reduction reaction catalysts with high specific and mass activities have been developed, promising to reduce the cost of proton exchange membrane fuel cells (PEMFCs). However, the high activities are mostly achieved in rotating disk electrode (RDE) measurement and have rarely been accomplished at the membrane electrode assembly (MEA) level [1].

One of the key reasons is the resistance caused by complex mass transport pathways, especially at higher current densities. The size and distribution of the ionomer aggregates in catalyst layers are found to be not uniform and easily affected by the concentration of the ionomer [2]. The proton transport is limited when there is no ionomer on the catalyst surface, while the oxygen transport is hindered when the ionomer film is too thick. Therefore, it is very important to control the ionomer distribution on the surface of catalysts.

We designed a research protocol as shown in the figure: mask the Pt surface with carbon monoxide (CO) to change its surface energy and subsequently control the ionomer arrangement in the catalyst layer. The Knudsen diffusion resistance and ionomer diffusion resistance results suggest that the mass transport in the catalyst layer was suppressed by blocking and ionomer lean, indicating micro-construction of the catalyst layer to increase the active Pt area such as the thin and uniform ionomer distribution is an effective solution.

References

[1] Fan, J.; Chen, M.; Zhao, Z.; Zhang, Z.; Ye, S.; Xu, S.; Wang, H.; Li, H. “Bridging the Gap between Highly Active Oxygen Reduction Reaction Catalysts and Effective Catalyst Layers for Proton Exchange Membrane Fuel Cells,” Nature Energy, vol. 6, no. 5, pp. 475-486, 2021.

[2] Cetinbas, F. C.; Ahluwalia, R. K.; Kariuki, N. N.; Myers, D. J. “Agglomerates in Polymer Electrolyte Fuel Cell Electrodes: Part I. Structural Characterization,” Journal of The Electrochemical Society, vol. 165, no. 13, pp. F1051-F105, 2018.

Figure 1
Lanthanide Vanadate: An Efficient and Stable Oxygen Evolution Reaction Catalyst for Enhanced Water-Splitting Applications
Authors: El Issmaeli Youness , Lahrichi Amina , Kalanur Shankara S. , Natarajan Sadesh Kumar , Pollet Bruno Georges
Published: February 2024

Hydrogen fuel production through water-splitting reactions offers a sustainable approach to store renewable energies. However, the efficiency of this process is impeded by the oxygen evolution reaction (OER), a complex four-electron oxidation half-reaction. In this study, we present a highly active and stable OER catalyst, lanthanide vanadate (LnVO4 - Ln = La to Lu), synthesized using a straightforward hydrothermal method. Comprehensive characterization of the electrocatalysts was performed employing scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) analysis. When applied to nickel (Ni) foam, lanthanide vanadate achieved a current density of 10 mA cm-2 at an overpotential of +280 mV in a 1.0 M KOH electrolyte. Furthermore, exceptional stability was demonstrated for over 5 hours of continuous operation. These findings highlight the potential of lanthanide vanadate-based materials as promising catalysts for efficient and stable overall water-splitting processes.
Recycled UHT Milk Carton Cellulose Substrate for Colorimetric and Electrochemical Sensor of Lactate
Authors: Phamonpon Wisarttra , Promphet Nadtinan , Ummartyotin Sarute , Rodthongkum Nadnudda
Published: February 2024

Recycled cellulose prepared from UHT milk carton waste was employed as a novel substrate for colorimetric and electrochemical lactate sensors to evaluate the milk quality. The cellulose is initially extracted by chemical method (alkali and bleach treatment) to prepare the dual-sensing substrate. For colorimetric sensor, an enzyme immobilization was performed on the recycled cellulose substrate prior to enhancing specificity for lactate detection. Subsequently, the recycled cellulose substrate was dipped in an aluminum solution extracted from aluminum foil from the packaging to create a conductive working electrode with improved surface roughness compared with recycled cellulose substrate, confirmed by atomic force microscopy. For the physical and chemical characterization, scanning electron micrograph demonstrated 3D fibrous network with the porous in between, and X-ray photoelectron spectroscopy presented the binding energy with the Al-O peak at 73.256 eV, verifying the existence of aluminum on the recycled cellulose substrate after surface modification. For the sensing performance, the colorimetric sensor provides the increasing purpleness intensity with the increment of lactate concentration, while the aluminum-modified recycled cellulose substrate exhibited the increased current response upon the increased lactate concentration. Furthermore, this dual-lactate sensor can offer a linearity of 0.125-2 M, covering a cut-off lactate level (1.0 M) for milk spoilage. Ultimately, this sensor is successfully utilized for lactate determination in real milk samples, showing its high efficiency as an alternative platform for milk quality evaluation.
Robust and Autonomous Space Weather Charge Mitigation Coatings
Authors: Radhakrishnan Rajeswaran , Vijapur Santosh Hanamant , Liu Danny , Hall Timothy , Inman Maria , Snyder Stephen , Dennison J R , Robertson Matthew
Published: February 2024

National Space Weather Strategy and Action plan calls for the need to enhanceProtection of National Security, Homeland Security, and Commercial Assets and Operations against Effects of Space Weather. Extreme space weather event like solar flares, cosmic rays, and radiation belts cause ionizing radiation that can damage electronics, solar arrays, and optical systems on satellites reducing their functionality and lifetimes, by inducing an ionic charge on the spacecraft’s surface, when a spacecraft fly in and out of the ionosphere. This negative charge buildup can lead to ion sputtering/arcing, and producing irreparable damage in spacecraft components. Therefore, the local application of materials systems that can passively mitigate the negative charge build up by emitting the electron back into space, while improving resistance to erosion during ion sputtering is of interest. Accordingly, Faraday Technology is developing a low-cost, efficient and scalable manufacturing process for the local deposition of lightweight passive highly emissive and erosion resistant coating onto spacecraft viable substrates that can mitigate charging and erosion effects from ionizing radiation. The composite coating showed a ~1500% increase in maximum (Emax) total electron yield over bare aluminum, extending by 4 times the range of electron yields between crossover energies >1, and demonstrated the potential for erosion resilience in modeled International Space Station plasma erosion conditions. The composite coating could be applied to various spacecraft platforms include spacecraft skin, solar arrays, circuit boards, and emitters such that their lifetime, effectiveness and durability within LEO/GEO environments events can be enhanced.

Acknowledgements:The financial support of NASA SBIR/STTR program through contract No.80NSSC22PB020 is acknowledged.
Hybrid Reactor by the Combination of Water Electolyzer with Methanation Reactor Targeting the Space and Terrestrial Applications
Authors: Sone Yoshitsugu , Shima Asuka , Mendoza-Hernandez Omar Samuel , Nakajima Hironori , Matsumoto Hiroshige , Inoue Mitsuhiro , Abe Takayuki
Published: February 2024

Japan Aerospace Exploration Agency (JAXA) collaborates with Toyama University and Kyushu University to create the hybrid system where the water electrolyzer is directly combined with Sabatier reactor shown in Fig. 1.

In order to generate oxygen, people use water electrolyzer. Under the micro-gravity condition, the specially designed gas-water separator is always needed to generate oxygen for breezing. The hydrogen which is the by-product from water electrolysis can also be used for the reduction reaction of carbon dioxide to generate methane and water. It is so called ‘Sabatier reaction’ which is very convenient for the water recovery in the closed environment.

In general, the Sabatier reaction can be triggered with maintaining rather high temperature above 300 degrees C. However, the conversion of the reaction should become higher at lower temperature since the reaction is exothermic.

We first focused our efforts to develop the catalysts which realizes the Sabatier reaction at around 200 degrees C.

We then tried to transfer the heat generated from the Sabatier reaction to the water electolyzer.

The novel internal structure of the water electolyzer was developed. Pressurized water without circulation is supplied to the water electrolyzer in which the interdigitated electrode locates. Water first contacts to the proton conducting electrolyte directly, and then diffuses to the electrode where the electrolysis reaction takes place. The electrode is covered with the hydrophobic materials so that only the gaseous material should pass through it without using any gas-water separation devices. The heat transferred from the Sabatier reaction enhances the efficiency of the water electrolysis reaction. By the combination, oxygen can be used for breezing, and hydrogen can be used for the reduction reaction of carbon dioxide to create water and methane as a unitized device.

We successfully demonstrated the performance of the tandem device where the water electolyzer is combined with Sabatier reactor through both experiment and mathematical modeling.

Acknowledgments

This work was partially supported by JST CREST and NEDO Green Innovation Fund Projects.

Figure 1
Deuterium Enrichment by PEM Water Electrolysis Using Water Circulation
Authors: Sato Ibuki , Matsushima Hisayoshi , Ueda Mikito
Published: February 2024

Artemis Project, an international space exploration project proposed by the United States and involving Japan, plans a long-term manned lunar exploration in the late 2020s. That project considers the capture of He3, a resource for fusion that does not exist on Earth. On the other hand, He3 is produced by the half-life of tritium (T). Now new hydrogen isotope separation is required for recovering T exhausted from nuclear reactors.

The water electrolysis is well known to enrich protium (H) in gas phase and, deuterium (D) and T in the electrolyte [1]. The modern electrolysis is performed by solid polymer membrane water electrolysis (PEMWE). However, there are few reported cases for the isotope separation by PEMWE. In this study for pursing high D separation, the optimization of the electrolysis system was investigated.

The initial D concentrations in the electrolyte were 10, 30, and 50 at% IrO2 was used as the anode catalyst and Pt/C as the cathode one. The electrolysis was galvanostatically conducted. Hydrogen gas was analyzed by a quadrupole mass spectrometer (Q-Mass) to determine the ratio of H2, HD, and D2. The electrolyte was analyzed by Fourier transform infrared spectrophotometer (FT-IR) to determine the ratio of H2O, HDO, and D2O.

Figure. 1 shows the schematic illustration of gas and water flow chart in experimental setup. Electrolyte was sent to the cell by the electric pump constantly. When the experiment was carried out, evolved gas and drained water was analyzed. The water out from the cell was returned into the electrolyte tank and electrolyzed repeatedly. The gas was introduced to Q-Mass. By using this circulation system, D was concentrated in the electrolyte efficiently . In this experiment, its concentration reached about 95at.%. To quantitatively evaluate the D enrichment by PEMWE, the separation factor α was calculated from the ratio of D concentrations in the electrolyte to the gas. The value of α was approximately 4.0. However, the valueslightly decreased above 90 at.% D. More detailed results will also be presented in our Poster, Abstract #176411.

Figure 1
(Invited) Case Studies for in-Space Electrochemical Operations
Authors: Hall Timothy , Wang Dan , Liu Danny , Moran Andrew , Vijapur Santosh Hanamant , More Santosh R , Garich Holly , Radhakrishnan Rajeswaran , Snyder Stephen , Inman Maria , Taylor Earl Jennings
Published: February 2024

Faraday Technology Inc. is a research, development and electrochemical engineering firm developing electrochemical innovations for terrestrial and space system.[1,2] With that founding basis Faraday has been able to bridge the gap between academic understanding and small-scale demonstrations to commercialization of practical components for over 32 years of operation.

This presentation will discuss a broad range of electrochemical approaches to improve the performance of components used in space or to be used for in-space production. We will provide insight into case studies, performed at Faraday, from our four business units of electrodeposition, electrochemical surface finishing, electrochemical conversion, and electrochemical system design. For instances, we will discuss direct print electrodeposition, electrophoretic application of coatings for glare resistance, surface finishing of rocket components, bioelectrochemical treatment of urine, and the generation of peroxide. Each electrochemical process has applications on earth and in space; additionally, each program had to overcome specific challenges that only space can present.

References:

J. Taylor “Adventures in Pulse/Pulse Reverse Electrolytic Processes: Explorations and Applications in Surface Finishing” J. Applied Surface Finishing,
3(4), 178-189 (2008).

J. Taylor, et al., (2019; Chapter 7) “Breaking the Chemical Paradigm in Electrochemical Engineering: Case Studies and Lessons Learned from Plating to Polishing” R.C. Alkire (Volume 18). Electrochemical Engineering: The Path from Discovery to Product.Wiley-VCH.
(Invited) Development of Binders, Surface Coatings and Electrolytes to Stabilize Silicon Anodes for Lithium Batteries
Authors: Lucht Brett L.
Published: February 2024

Silicon is a desirable anode material for lithium ion batteries due to the high lithiation capacity of silicon. However, the lithiation/delithiation process results in large volumetric changes to the silicon particles. The volumetric changes result in instability of the solid electrolyte interphase (SEI) on silicon. Investigations of the effect of binders, surface modifying agents and electrolyte formulations on the stability of the SEI on silicon anodes will be presented. Methods to modify the silicon interface to improve cycling performance will also be discussed.
(Invited) Advanced Fluoropolymer Binder for Solvent-Free Manufacturing of Lithium-Ion Battery Electrodes
Authors: Xun Shidi , Aryal Shankar , Waters Crystal , Upasani Tejas
Published: February 2024

With rising demand of lithium-ion batteries for consumer electronics and electric vehicles, battery manufacturers are eager to increase energy density, reduce cost of manufacturing and minimize environmental footprints. Solvent-free electrode manufacturing technology has advantages over conventional wet electrode casting methods. It can save the cost of solvent, reduce energy consumption associated with drying off the solvent and eliminate capital investment for solvent recovery facilities. It also can reduce the environmental impact and mitigate health concerns of organic solvents, such as N-methyl-2-pyrrolidone, used in wet slurry process. In addition, the solvent-free process enables manufacturing of high-quality thick electrodes; This is challenging for wet slurry process due to the sedimentation of particles and redistribution of binders during drying. Teflon™ PTFE fluoropolymer is the top binder candidate for a solvent-free electrode process due to its strong fibrillation property. The fibrils provide the binding force necessary to maintain the structural integrity of electrodes and make it feasible to scale up a roll-to-roll production process.

Chemours is a global market leader in advanced fluoropolymers with strong capabilities in molecular design, synthesis, scale-up and manufacture; This ensures the delivery of the high-quality products to meet customer needs. In this presentation, we will give an overview of Chemours advanced fluoropolymer products for solvent-free manufacturing of anode and cathode electrodes. By tailoring the physical and chemical properties of fluoropolymers, electrode processibility and battery performance can be significantly improved.
(Invited) Challanges with Novel Binders for LiNi0.5Mn1.5O4
li-Ion Battery Electrodes
Authors: Mathew Alma , Heiskanen Satu Kristiina , Lacey Matthew , Younesi Reza , Brandell Daniel
Published: February 2024

In the search for high-energy density Li-ion battery electrode materials which are also comparatively sustainanble, LiNi0.5Mn1.5O4 (LNMO) is often targeted as a promising next-generation alternative. While the capacity of LNMO is limited, it has a high operating voltage around 4.7 V vs. Li+/Li, and the spinel structure of the materials renders useful power capacilities. Moreover, it is a cobalt-free cathode. However, fabricating functional electrodes have shown problematic due to inherent instabilities at both bulk and surfaces, where especially operation at elevated temperatures has shown to cause capacity degradation. Problems comprise structural changes, loss of oxygen, and Mn dissolution, often interconnected with each other. One strategy to improve stabilization would be through coatings of the LNMO particles, either inorganic or organic.

The polymer binder used for battery processing is inherently an organic coating layer, since it wraps around the particles of the electrodes. Thereby, binders has been shown to being able to add functionalities to electrode materials, e.g. to improve electronic conductivity, add storage capacity or mitigate side-reactions. The binder is at interplay with the reactions causing interphase layer formation. Thereby, changing or taioring the binder can cause direct improvements in cell performance.

Poly(vinylidene difluoride) (PVdF) and its many derviates is since long time the standard for Li-ion battery electrodes, despite not being particular sustainable and being dependent on toxic solvents such as N-methyl-2-pyrrolidone (NMP). LNMO is, in this context, no exception. Nevertheless, while PVdF is chemically intert, it provides little other capabilities to the battery electrodes, and other binder systems could improve in this context: either through electochemica performance or through being more sustainable.

Here, two other binder systems for LNMO are discussed: polyacrylonitrile (PAN) and polyacrylic acid (PAA). Polynitriles are often promoted as being comparatively stable at higher potentials, while also being ionically conductive, and should therefore in principle add functionalities into the resulting electrodes. PAA, on the other hand, has shown good adhesion and adherence to oxide surfaces, and can thereby form more robust interfacial layers on the cathode. We show here, however, that challenges remain for these alternative binder systems, not least due to the high operating potential of LNMO electrodes which cause side-reactions of both types of alternative binders. These side-reactions are their products are analyzed through a range of methods, e.g. photoelectron spectroscopy, electron microscopy and electroanalytical techniques, thereby providing guidance to the development of novel binders for high-voltage electrodes.
(Invited) Design of Application of Low Tortuosity Electrode for Lithium Batteries
Authors: Xie Jia , He Renjie , Tian Gangling
Published: February 2024

Pursuing high Energy density and high power density are highly desirable for lithium batteries to better meet unmet needs in energy storage applications. Yet traditonal materials and electrode architectures are approaching the therotical limits of lithium batteries. Moreover, it is difficult for porous electrodes manufactured by roll to roll process to simoutaneously achieve both high energy denisty and high power denisty. Here, we report current research progress of lithium batteries with low tortousity electrodes including natural wood-based elctrodes with aligned straight channels, ice-template based electrodes and their applications in layer oxides, lithium-ion phorsphate and lithium-sulfur batteries. It is shown that low tortuosity electrodes lead to performance improvements in energy density, power density as well as cylcing life, which could have tremendous impact on advancing lithium battery technology.
Redox Shuttle Additives for Sodium-Ion Batteries
Authors: Das Dhrubajyoti , Nagmani . , Kumar Ananya , Puravankara Sreeraj
Published: February 2024

Redox shuttle additives are already known in the battery field to provide overcharge protection, mainly at high-voltage cathode electrodes. The electroactive species can get either oxidized at the cathode side or reduced at the anode side, preferentially during the battery cycling. The mechanism involves the generation of positively charged radicals during oxidation and the subsequent diffusion and reduction at the anode surface. This shuttling process continues between the electrodes through baseline electrolytes. Redox shuttle additives are extensively studied in Li-ion batteries (LIBs).1–3 Benzophenone (BP) is one of the redox shuttle additives used successfully in lithium-ion batteries.4 No report exists in the literature for BP additives in sodium-ion batteries (SIBs).

This work investigates BP (an already known overcharge protecting additive) and substituted 4-methyl BP (4-methyl benzophenone) as an electrolyte additive in baseline electrolyte containing NaClO4 in EC/PC solvent on both electrodes. The aim is to investigate BP's SEI-forming properties in sodium-ion batteries. The initial half-cell test with a Hard Carbon anode without and with 0.5 wt% 4-methyl BP as the additive is shown in Fig.1. 4-Methyl BP additive shows a large increase in specific capacity from 337 mAh gm-1 to 438 mAh gm-1 at 0.1C rate in a 5 mV - 1.5 V voltage range. The oral presentation will focus on the effect of additive concentration on the battery performance of HC and polyanionic cathode NVP in half-cell and full-cell configurations in Na-ion batteries.

References:

C. Buhrmester, L. Moshurchak, R. L. Wang, and J. R. Dahn, J. Electrochem. Soc., 153, A288 (2006).

L. M. Moshurchak et al., J. Electrochem. Soc., 156, A309 (2009).

M. Tang and J. Newman, J. Electrochem. Soc., 158, A530–A536 (2011).

Q. Wang, S. M. Zakeeruddin, I. Exnar, and M. Grätzel, Electrochem. commun., 10, 651–654 (2008).

Figure 1
A Protocol for Predicting Lithium-Ion Battery Performances Reflecting the Three-Dimensional Structure of Electrodes
Authors: Mandai Toshihiko , Nishikawa Kei , Inoue Gen , Kanamura Kiyoshi
Published: February 2024

As social needs for higher capacity and longer life of lithium-ion batteries increase, shortening the period from research to development and commercialization of batteries has become an extremely important issue. To minimize the above period, a protocol for predicting the performances of (lithium-ion) batteries is highly urged for. Many reports have been published so far regarding the simulation technology of charge-discharge profiles of lithium-ion batteries.1,2 However, in most of simulations, the porous structure of lithium-ion battery electrodes is simplified into a 1D or 2D models. To achieve more accurate battery performance prediction, we adopted the actual 3D structure of the positive and negative electrodes of lithium-ion batteries in simulations.

A plasma FIB SEM (Helious5, Thermofisher Scientific Inc.) was used to obtain the 3D structures of the positive and negative electrodes of the lithium-ion battery. The porosity and tortuosity of the electrodes were calculated by reconstructing a 3D image and performing image analysis. Based on this 3D structure, we also calculated the lithium ion conductivity in the electrode. The obtained 3D structural parameters were applied to the simulation of battery characteristics and compared with actual charge/discharge test results. We have also developed a performance prediction protocol that allows to reflect the measured physical properties of battery materials in the simulation.

Figure 1 shows cross-sectional images of two different high-nickel-type positive electrodes prepared under different experimental conditions. It can be seen that the active materials are packed densely for both the electrodes, but the level of conductive carbon and binder dispersion is different. The particle size distribution of the active materials was also found to be largely different between the two samples. Structural parameters were obtained from the 3D structure by image analysis, and highly accurate performance prediction was performed. It can be predicted that the rate capability reflects the structural homogeneity. Also, the simulation revealed that the particle size distribution plays an important role for achieving favorable rate capability.

Acknowledgement

This work was financially supported by the NEXT Center of Innovation Program (COI-NEXT, Grant Number JPMJPF2016) of the Japan Science and Technology Agency.

References

(1) M Doyle , J. Newman, A. S. Gozdz, C . N. Schmts, and M. Tarascon, J. Electrochem. Soc. 1996, 143, 1890

(2) G. Li and C. W. Monroe, Annu. Rev. Chem. Biomol. Eng. 2020, 11 277.

Figure 1
Multi-Functionalized High Ionic Conductive Soft Matter for Separator-Free All Solid-State Lithium-Ion Battery
Authors: Wang Fu-Ming
Published: February 2024

Solid state battery (SSB) with its promising advantages such as extreme light weight, thin film manufacturing, and compact structure, which leads to a possibility of high energy density design (up to 400-500 Wh/kg). The most important key for the development of SSB is the solid electrolyte (SE). Nowadays, there are several SEs been studied to overcome many drawbacks that are being investigated. Those problems are low ionic conductivity at room temperature, low electrochemical stability, low interfacial compatibility, and low mechanical property, respectively. Although several SEs like sulfide, halide, oxide, and polymer-based materials are developed, but there are still big challenges for further commercialization.

In this research, multi-functionalized high ionic soft matters have been synthesized successfully. These soft matters are siloxane polyelectrolytes that contains two functions of single ion transfer and lithium-ion compensation. With the single ion transfer design, the ionic conductivity of siloxane polyelectrolyte is achieved to 4*10-4 S/cm at room temperature and the electrochemical stability is illustrated to a window of 0-5.5V. This soft matter provides outstanding interfacial compatibility to solid-solid interface owing to its unique function of lithium-ion compensation by directly coverage on cathode active materials. According to the results, the impedance of SSB with siloxane polyelectrolytes is decreased by 50% as well as the initial capacity on NMC811 cathode is 213.3 mAh/g (CE: 91.4%). The cycle ability on this separator-free polymer based SSB shows almost no fading in 50 cycles (at 60oC) without any assistances, the SSB only has NMC811 cathode, SE, and lithium metal anode. Fig. 1 shows the SEM images of pristine and siloxane polyelectrolyte covered NMC811. According to the results, the NMC811 is homogeneously covered by thin film siloxane polyelectrolyte, which is used to transfer lithium ions.

This research demonstrates a separator-free all SSB by multi-functionalized siloxane polyelectrolyte. High ionic conductivity, high interfacial compatibility, lithium-ion compensation, and high mechanical property are provided to a future high energy density battery.

Figure 1
Interfacial Layers to Enable Recyclability of All-Solid-State Lithium Batteries
Authors: Lan Yi-Chen , Gomez Enrique Daniel
Published: February 2024

All-solid-state batteries (ASSBs) with lithium metal anodes are promising energy storage devices due to their high energy density and safety. Their potential massive production and lack of recycling methods necessitate the development of strategies to address the problem of spent batteries. Current recycling methods rely on organic solvents or high-temperature furnaces, which are not environmentally friendly. Here, we proposed a design for recyclable all-solid-sate lithium batteries by introducing interfacial layers at electrode interfaces. Flexible lithium perchlorate doped polypropylene carbonate (PPC-LiClO4) thin-films improve contacts between metallic lithium and Li7La3Zr2O12 (LLZO)-based composite electrolytes, LLZO–PPC–LiClO4, thus lowering interfacial resistance. Half cells with modified interfaces exhibit a critical current density of 1.0 mA cm−2 and outstanding cycling stability at a current density of 0.1 mA cm–2. In addition, polymer-salt layers serve as sacrificial layers to enable clean separation of cathodes and solid-state electrolytes. Recovered cathodes and composite electrolytes show high purity of LiFePO4 and LLZO ceramic materials that allows further direct recycling.
(Invited) Potentiometric Entropy Measurements and Isothermal Operando Calorimetry to Identify the Charging Mechanisms of Battery Materials
Authors: Pilon Laurent
Published: February 2024

This talk presents recent development in potentiometric entropy measurements and isothermal operando calorimetry to gain insight into the charging mechanisms of lithium ion batteries. First, the concept, design, and operation of two unique experimental apparatuses will be presented. Then, the effects of material composition, crystallographic structure, and particle size on the cell’s thermodynamic behavior, polarization, and lithium ion transport will be discussed for different Wadsley-Roth materials (e.g., TiNb2O7, PNb9O25, (W0.2V0.8)3O7) under quasi-equilibrium conditions. Particular attention will be paid to phase transition, lithium ion intercalation and ion ordering in solid solution, and/or two-phase coexistence occurring during charging/discharging. Finally, instantaneous heat generation rates measured by isothermal operando calorimetry at each electrode will be used to identify the causes of energy dissipation and to provide insight into the transport and interfacial phenomena taking place in the electrodes at different states of charge and charging rates. Here, special emphasis will be placed on the contributions of Joule heating associated with resistive losses, heat of mixing due to ion concentration gradient, and reversible entropic changes.
3D Electrothermal Model for Internal Temperature Distribution in Lithium-Ion Battery Cell and Module
Authors: Tardy Erwan , Thivel Pierre-Xavier , Druart Florence , Kuntz Pierre , Devaux Didier , Bultel Yann
Published: February 2024

In recent years, lithium-ion batteries (LIBs) have been massively developed in many applications as they provide high energy and power densities, high efficiency and long lifespan compared to other battery technologies. Despite remarkable improvements, Li-ion batteries still face thermal issues, which cause performance drop, limited calendar life, safety concerns and temperature-caused degradation. Therefore, proper thermal management for a LIB is necessary to control its temperature and to extend its lifetime. Internal temperature measurement remains very challenging for LIB. So, electrothermal LIB models, developed to forecast both electrical performances and temperature distributions, seems to be a powerful and complementary tool to experiments, in particular to obtain battery temperatures in use. Most of models, assume simplified approach considering that heat sources are either located in the center of the cell or uniformly distributed in the volume of the cell and so do not consider the real internal geometry of the cells.

In this work, a 3D electrothermal model of a large commercial prismatic NMC-type lithium-ion cell (25 Ah) is developed based on the internal geometry reconstructed from tomography. The electrothermal model, developed with the COMSOL Multiphysics® software with the real internal geometry as well as the anisotropy of the thermal properties, accounts for irreversible and reversible heat sources. The entropy variation profiles were estimated by Entroview™ using their patented method. The validation of the model is performed thank to temperature measurement during charge and discharge at several currents in a climatic chamber at 25°C. Simulation results highlight exothermal and endothermal behaviors related to the entropy change along with the charge and discharge stages. Moreover, the internal temperature distribution is thoroughly impacted by the internal geometry of the cell and the anisotropy of the thermal properties.

Finally, the 3D electrothermal model is extended to a module of 12 cells in series (12S) to evaluate the heterogeneities of internal temperatures considering the real geometry of each cell. Once validated, simulation (as shown of figure 1) underline the heterogeneous temperature distribution at the module scale and the importance of having an efficient battery thermal management system to limit an excessive increase of the temperatures which can cause performance drops until irreversible degradations.

Figure 1
(Best Presentation Award - 1st Place) Cyclic Aging Study of Commercial Li-Ion Batteries Focusing on Temperature
Authors: Cloos Lisa , Queisser Oliver , Wetzel Thomas
Published: February 2024

It is well known that temperature significantly impacts the cyclic aging behavior of Lithium-ion batteries. Temperatures outside the recommended optimum range promote different aging mechanisms. However, the temperature dependency of these aging mechanisms might also vary for different cell chemistries used in commercial Li-ion battery cells. Additionally, due to heat generation inside the cell and the cooling strategies in the applications the temperature field inside the cell is most likely inhomogeneous. This has led to several cyclic aging studies looking into these non-homogeneous temperature fields [1–4]. Hunt et al.[4] observed more pronounced aging for surface cooled cells, which they attributed to through-plane thermal gradients. Werner et al.[1,2] found no acceleration of the aging behavior for the applied in-plane thermal gradients compared to homogeneously aged cells. For thermal transients both Werner et al.[1,2] and Carter et al.[3] found faster aging in some cases.

Few cyclic aging studies have been done on the impact of more complex temperature boundary conditions. These studies involved very few cell chemistries and more research is needed. A test was set up and preliminary results of a cyclic aging study on commercial Lithium-ion battery cells can be presented. Multiple parameters, such as capacity and resistance, are evaluated and compared to reference cells, which are cycled at a standard, homogeneous temperature.

Werner et al. (2020) Inhomogeneous Temperature Distribution Affecting the Cyclic Aging of Li-Ion Cells. Part I: Experimental Investigation. Batteries 6:13. https://doi.org/10.3390/batteries6010013

Werner et al. (2020) Inhomogeneous Temperature Distribution Affecting the Cyclic Aging of Li-Ion Cells. Part II: Analysis and Correlation. Batteries 6:12. https://doi.org/10.3390/batteries6010012

Carter et al. (2019) Detection of Lithium Plating During Thermally Transient Charging of Li-Ion Batteries. Front Energy Res 7. https://doi.org/10.3389/fenrg.2019.00144

Hunt et al. (2016) Surface Cooling Causes Accelerated Degradation Compared to Tab Cooling for Lithium-Ion Pouch Cells. J Electrochem Soc 163:A1846-A1852. https://doi.org/10.1149/2.0361609jes
(Invited) Sensor Integration in Lithium-Ion Cells from a Systems Perspective
Authors: Schmidt Jan Philipp
Published: February 2024

The cell temperature is a critical factor that impacts performance, safety and longevity of batteries. For the optimum operating strategy, therefore, maximum and minimum cell temperature must be available to the BMS at all times. This is a challenge, however, because typical automotive batteries use more than a hundred cells and the cells themselves do not exhibit a homogeneous temperature.For this reason, it was and is particularly important in the development of lithium-ion batteries to measure the temperatures at the relevant points - and thus often also inside the cells themselves.

In the first part, an overview of the current state of research on cell-internal temperature measurement will be given and the efforts to transfer these approaches into application will be further discussed. In particular, the technical requirements at the system level will be discussed, but also the difficulties of industrialization.

In addition to the integration of sensors, the determination of temperature from already existing variables such as cell voltage and current has already been described in many approaches. In particular, the application of impedance spectroscopy has reached a level that can be described as ready for industrialization. After an overview of the current state of research, the requirements for application in the target system will be addressed and the necessary further research is discussed.
Predicting the Heat Generation Rate in Large Format Pouch-Type Lithium-Ion Battery Cells for Automotive Applications
Authors: Zhang Han , Garrick Taylor R. , Labaza Christine , Gao Jing , Koch Brian , Du Xiaoniu , Choi Chihwan , Choe Song-Yul
Published: February 2024

Accurate prediction of the heat generation rate of lithium ion batteries is critical for driving towards a cost effective and efficient design of a thermal management system for various applications.[1, 2] because of the increase in battery cell dimensions associated with an increase in battery cell capacity to drive towards a reduction in range anxiety for automotive applications, as well as more aggressive operating conditions that are typically seen in the automotive industry, such as direct current fast charge and sustained driving under load, heat generation at the cell level must be considered as spatially nonuniform during operation. Proper design of the thermal management system requires prediction[3] of the heat generation of the battery cell in both a lumped fashion for system sizing, as well as a distributed mode in order to focus cooling appropriately to decrease local temperature extremes. Local temperature extremes can adversely affect the aging of the battery cell due to the non-uniformities in electrochemical utilization of the active material, increased local reaction rates, and increased mechanical stresses in active materials.

In this work, we detail our efforts to characterize the heat generation[4] of a battery cell under a variety of operating conditions, quantify the impact of temperature non-uniformities[5] on the aging of the battery cell, and experimentally[6, 7] evaluate the localized aging in the battery electrodes based on local temperature conditions. Here, we will describe the modeling methods developed to link operating conditions, aging, and heat generation with the electrochemical performance of the battery cell. A discussion of the model performance for relevant automotive applications will also be included.

References

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