bluuebunny/crossref_metadata_2025_split huggingface dataset:
Unraveling Plasmonic Effects in Plasmon-Enhanced Lithium–Oxygen Batteries
Authors: Chae Kyunghee , Kim Minju , Marques Mota Filipe , Kim Dong Ha 
Published: February 2024

Rechargeable lithium–oxygen batteries have high theoretical energy density compared to the conventional Li–ion batteries. However, the recharging process is primarily disturbed by the large overpotential caused by sluggish OER kinetics. Plasmonic materials have unique properties with light, known as surface plasmon resonance (SPR). In this study, we demonstrate plasmonic effect in the Li–O2 battery system by incorporating gold nanoparticles on the Ketjen Black (KB) cathode. During discharge, plasmonic Au NPs induce a Li2O2 morphology change to small particles, which are easily decomposed during recharge. Most importantly, the SPR-induced hot carriers help to form and decompose Li2O2 and suppress carboxylate side-products, decreasing recharge voltages and increasing the round-trip efficiency up to 80.2%. Meticulous analyses of the catalytic properties of the Au NPs and the SPR-induced near-field enhancement and local heat effects are here additionally shared.
Keywords: Li–O2 battery, Plasmonics, Light-enhanced batteries, Hot carriers, Near-field enhancement
Electrochemical Model-Based State-Space Approach for Real-Time Parameter Estimation of Lithium-Ion Batteries
Authors: Cho Kyeongeun , Kim Sanghyun , Kim Seongyoon , Choi Jung-Il 
Published: February 2024

Lithium-ion batteries are widely used in various applications, including electric vehicles and renewable energy storage systems, due to their high energy density, long cycle life, and low self-discharge rate. Accurate estimation of battery state of charge (SOC) and state of health (SOH) is crucial for their safe and efficient operation.
In this study, we propose a model-based state-space solver for real-time monitoring of lithium-ion batteries under various operating conditions. The state-space model simplifies a single-particle model and enables simulations considering the current state of the battery using a Kalman filter. The model includes a one-dimensional Single Particle Model with Electrolyte (SPMe) and uses eigenfunction expansion to solve the mass conservation equation for the electrolyte phase. The final form of the state-space model for the solid and electrolyte phase includes a voltage equation using lithium-ion concentration. The proposed solver was validated by comparing it with the SPMe solver, and the results agree well.
To achieve on-line updating of the battery model parameters, we propose a multi-scale parameter adaptive method based on dual Kalman filters for estimating the SPMe model parameters. The fast time-varying parameters are separated from the slowly time-varying parameters, and then each group is estimated by a different Kalman filter with a different time constant. This method enables the estimation of both the SOC and all parameters, including the SPMe model parameters. Additionally, we provide a parameter adjustment method for dual extended Kalman filters when estimating multiple parameters.
The proposed method reduces the influence of the initial state error on the algorithm and improves its robustness. Experimental results demonstrate that the accuracy of the algorithm is improved by separating the fast and slow parameters and estimating them with different Kalman filters. The proposed solver can be used with Kalman filters and the like in an onboard environment due to its fast calculation speed.

Figure 1
Highly Fluorinated and Boron Containing Anion Derived Stable Anode and Cathode Interfaces for Long Cycle and High Voltage Sodium Metal Batteries
Authors: Lohani Harshita , Duncan Dale , Kar Mega , Kumari Pratima , Mitra Sagar 
Published: February 2024

Sodium metal is a propitious anode for the development of next generation metal batteries owing to its low reduction potential (-2.71 V) and high theoretical capacity (1165 mAh g-1)1. Among various electrolytes, carbonate solvents can be useful to develop high voltage metal batteries with wide temperature range2. However, the aggressive reactivity of sodium metal in carbonate electrolytes lead to the formation of unstable solid electrolyte interface on the metal anode which renders poor long cycling performance to the battery3. In this work, we have fabricated thin and inorganic components (F and B rich) rich solid electrolyte interface (SEI) on Na metal anode and cathode electrolyte interface (CEI) on oxide-based cathode to improve long cycling stability of sodium metal battery. Here, fluorine (F) and boron (B) containing anion is compared with conventional hexafluorophosphate anion (PF6-) in binary carbonate solvent system (EC:EMC). The stable stripping/plating behaviour of both symmetric (Na/Na) and asymmetric cell (Al/Na) in case of F and B containing anion is found compared to the PF6
- anion.
The excellent long-term cycling stability of full cell (Na/Na0.67Fe0.5Mn0.5O2) is further attributed to the improved electrochemical stability window and better aluminium passivation on employing F and B containing anion in the electrolyte system as compared to PF6
- anion. The dual role of F and B containing anion to form stable interfaces on both the anode and cathode side provides a pathway in the development of fluorinated electrolytes for high voltage sodium metal batteries.
References:
(1) Yang, T.; Luo, D.; Liu, Y.; Yu, A.; Chen, Z. Anode-Free Sodium Metal Batteries as Rising Stars for Lithium-Ion Alternatives. https://doi.org/10.1016/j.isci.
(2) Xu, G.; Huang, S.; Cui, Z.; Du, X.; Wang, X.; Lu, D.; Shangguan, X.; Ma, J.; Han, P.; Zhou, X.; Cui, G. Functional Additives Assisted Ester-Carbonate Electrolyte Enables Wide Temperature Operation of a High-Voltage (5 V-Class) Li-Ion Battery. J Power Sources
2019, 416, 29–36. https://doi.org/10.1016/j.jpowsour.2019.01.085.
(3) Akkisetty, B.; Dimogiannis, K.; Searle, J.; Rogers, D.; Newton, G. N.; Johnson, L. R. Enflurane Additive for Sodium Negative Electrodes. ACS Appl Mater Interfaces
2022, 14 (32), 36551–36556. https://doi.org/10.1021/acsami.2c06502.
Synthesis and Electrochemical Characterization of Novel Electrolyte Additives for High Performance in Lithium-Ion Batteries with Si-Based Anodes
Authors: Schmidt-Meinzer Noah , Krossing Ingo 
Published: February 2024

Silicon is a promising active material for the anode in lithium-ion batteries (LIB), since it enables much higher energy densities than graphite - the state-of the art material for LIB-anodes. However, the utilization of silicon brings many challenges, which originate mainly from the enormous volume change between the lithiated and delithiated state (300%). One of the consequences is a constant re-formation of the solid electrolyte interphase (SEI), which is accompanied by a loss of active Li+. This leads to a strong capacity fading, which results in a very short cycle life. [1]
An efficient and economical approach to tackle these problems is the utilization of additives in the electrolyte. Additives are small molecules or salts that decompose during the first cycles of the battery life resulting in an interphase with modified composition and thereby an improved SEI. Depending on the additive the SEI can reduce the impedance of the cell and help to maintain the structural stability of the anode. [2]
In this work four new additives were synthesized and electrochemically tested with a silicon-based anode. Improvements regarding capacity retention were found for all additives in half-cell measurements. Hence, after 500 cycles additive 1 showed a 26 % increased capacity retention, while additive 4 induced an improvement of 43 % compared to the base electrolyte. Electrochemical impedance measurements were conducted and simulated directly after the formation as well as after 100 cycles. The resistance of the first semi-circle showed a reduction of 40 % and 26 % after formation and 100 cycles respectively, when the additive 1 is used. The second semi-circle showed no significant change after formation, but a 27 % reduction of resistance after 100 cycles, when the additive 1 is used. The semi-circles can be attributed to the Li ion migration in the SEI. Therefore, the SEI build from the decomposition of additive 1 favours charge-transfer compared to the SEI build from the base electrolyte. Scanning electron microscopy (SEM) images of lithiated and delithiated electrodes show smaller cracks on the surface when using additive 1 compared to the electrode treated with the base electrolyte. This phenomenon shows an increased cohesive force of the new formed SEI mitigating the effects of the enormous volume expansion in the electrode.
[1] Zuo X., Zhu J., Müller-Buschbaum P. & Cheng Y.-J. Silicon based lithium-ion battery anodes: A chronicle perspective review. Nano Energy. 31, 213-143; 10.1016/j.nanoen.2016.11.013 (2017)
[2] Eshetu, G.G., Zhang, H., Judez, X. et al. Production of high-energy Li-ion batteries comprising silicon-containing anodes and insertion-type cathodes. Nat Commun
12, 5459; 10.1038/s41467-021-25334-8 (2021)

Figure 1
Two Dimensional Pb-F-Cl and Ba-F-Cl As Supercapacitor Electrode Materials
Authors: Servottam Swaraj , Rao Chintamani Nagesa Ramachandra 
Published: February 2024

Two-dimensional (2D) materials have gained great importance since the discovery of graphene. Of these several 2D materials, PbFCl and BaFCl, have not been exploited for electrochemical applications. Herein, we have prepared single and few-layered nanosheets of PbFCl and BaFCl by exfoliation through ultrasonication in different solvents such as water, dimethylformamide and N-methyl-2-pyrrolidone. The Hansen-Solubility-Parameters of the solvents played an important role in exfoliation of bulk phase of PbFCl and BaFCl. These materials were studied for supercapacitor properties by means of cyclic voltammetry (CV) curves, galvanostatic charge–discharge (GCD) curves and electrochemical impedance spectroscopy (EIS). Exfoliated 1–2 layered PbFCl exhibits a high-specific capacitance of 158 F g−1 at a scan rate of 10 mV s−1.
References: -

Geim, A. K. & Novoselov, K. S. The rise of graphene. Nat. Mater.
6, 183 (2007).

Manjunath, K., Servottam, S., Soni, A. & Rao, C. N. R. A study of two-dimensional PbFCl and BaFCl. Bulletin of Materials Science
43, 1–7 (2020).
High-Capacity Nickel-Based Layered Oxides Containing Niobium Ions for Lithium-Ion Batteries
Authors: Yamaki Saeka , Ugata Yosuke , Yabuuchi Naoaki 
Published: February 2024

Lithium-ion batteries have been widely used in recent years, from portable electronic devices to electric vehicles. Although LiNiO2, is expected to be ideal electrode materials for electric vehicle applications due to its high reversible capacity, Ni ions migrate from octahedral sites of transition metal layers to tetrahedral sites of adjacent Li layers during charging. This process is partly reversible process but Ni ions are left the tetrahedral sites of the Li layer after the continuous cycle test, which prevents the re-insertion of Li ions, resulting in capacity degradation. [1]
To suppress the capacity degradation LiNiO2, the effect on the phase transition behavior by Nb substitution for Ni ions in LiNiO2 is examined.
The samples with different Nb contents LixNi1–xNbxO2, are synthesized and tested as electrode materials. The Nb-substituted sample shows highly improved cycle characteristics compared with non-substituted LiNiO2. SEM observation of the samples reveals that the primary particles become smaller, suggesting that the Nb-substituted influences the crystallization process for LiNiO2. By comparing the results of electrochemical and structural characterizations for the samples with or without Nb substitution, the origin of the improvement of electrode reversibility is discussed in details.
Reference [1] N. Ikeda et al., and N. Yabuuchi, Journal of Materials Chemistry A, 9, 15963 (2021).
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
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.