bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) Innovation in Electrocatalysis: Magnetoelectrocatalysis
Authors: Leddy Johna
Published: December 2024

Electrochemical processes are less energy intensive than thermal processes, especially for inner sphere reactions such as HER (H2 evolution reaction), HOR (H2 oxidation reaction), OER (O2 evolution reaction), ORR (O2 reduction reaction), CO2RR (CO2 reduction reaction), and NH3 generation. Energetic costs and environmental burdens are lowered electrochemically, provided an appropriate electrocatalyst can be identified. Often, electrocatalysts are identified through edisonian surveys.

Here, a more fundamental approach to identifying catalysts is posed as magnetoelectrocatalysis. Magnetic gradients drive electron transfer reactions across the electrode solution interface. This increases rates and efficiency, to lower energetic and environmental taxes. Demonstrated magnetoelectrocatalysis is presented for HER [1,2], ORR [3-5], and single carbon species electrochemistry including CO2RR [6].

Fundamental approaches to identifying effective magnetoelectrocatalysts are presented.

The financial support of the National Science Foundation (NSF CHE-1309366; CHE-0809745) and the Army Research Office (W911NF-19-1-0208 (74912-CH-II), DAAD19-02-1-0443, and several STTRs) are acknowledged.

References

Krysti L. Knoche Gupta, Heung Chan Lee, and Johna Leddy, “Magnetoelectrocatalysis: Evidence from the Hydrogen Evolution Reaction,” ACS Phys. Chem Au (2024), 4(2) 148–159, https://doi.org/10.1021/acsphyschemau.3c00039.

Kasun S.R. Dadallagei, Daniel L. Parr IV, Joshua R. Coduto, Andrew Lazicki, Sidney DeBie, Christian D.Haas, and Johna Leddy, “New Perspectives from Classical Transition State Theory: The Hydrogen Evolution Reaction on Metal Electrodes,” Journal of the Electrochemical Society (2023) 170(8) 086508; https://doi.org/10.1149/1945-7111/acf246.

Krysti L. Knoche Gupta, Nadeesha P. W. Rathuwadu, and Johna Leddy, Communication—Voltammetry of Lanthanide (III) Triflates Accessible in Acetonitrile at Nafion Modified Electrodes, Journal of the Electrochemical Society (2021) 168(6) 066511, https://iopscience.iop.org/article/10.1149/1945-7111/ac0649.

J. Leddy and K. L. Knoche, “Lanthanide electrochemistry,” US Patent 10,196,749, February 2019, Assignee: Johna Leddy, https://patents.google.com/patent/US10196749.

J. Leddy and K. L. Knoche, “Lanthanide electrochemistry,” US Patent 10,081,873, September 2018, Assignee: Johna Leddy, https://patents.google.com/patent/US10081873.

J. Leddy and N. P. W. Rathuwadu, “Carbon dioxide reduction and carbon compound electrochemistry in the presence of lanthanides,” US Patent 10,774,430, September 2020, Assignee: Johna Leddy, https://patents.google.com/patent/US10774430.
Unique Photothermal Material: Copper Phosphate (Cu3P2O8) with Broadband Visible-to-Near-Infrared Absorption Properties for Efficient Solar Steam Generation
Authors: Lee Jong Ho , Tatachari Santhanagopalan Shridharan , Tan Runfa , Sivanantham Arumugam , Cho In Sun
Published: December 2024

Harnessing renewable solar energy in interfacial solar steam generation (ISSG) can address global freshwater scarcity. Herein, we present copper phosphate (Cu3P2O8; CuPO) as a novel photothermal material with broad visible-to-near-infrared (Vis-to-NIR) absorption capabilities, suitable for interfacial solar steam generation (ISSG). CuPO demonstrates broad light absorption across a wide spectral range of 500–2200 nm, low thermal conductivity (0.64 W/m⋅K), high photon-to-heat conversion efficiency (87.9%) and possesses excellent hydrophilicity. Under simulated solar irradiation (AM1.5G, 100 mW/cm2), the CuPO photothermal absorber exhibited significant performance in water evaporation, achieving a rate of 2.05 kg/m2⋅h and efficiency of 95.0%. Significantly, the introduction of an ultraviolet cutoff filter (< 450 nm) highlighted a considerable contribution of near-infrared absorption by CuPO, accounting for over 80% of its total performance. The CuPO membrane maintained durable ISSG performance over 25 cycles, demonstrating its robustness. To conclude, our results lay the groundwork for cost-effective, high-performance ISSG systems using copper-based oxides. Our findings represent a significant step towards sustainable and accessible freshwater production solutions.

Keywords: Copper phosphate, Triclinic structure, Broadband light absorption, Vis-to-NIR, Low thermal conductivity, Interfacial solar steam generation
Interfacial Phase Separation Governs the Chemomechanics of Polymer Electrolytes in High-Voltage, Solid-State Lithium Batteries
Authors: Min Jungki , Bak Seongmin , Pietra Nicholas , Xia Dawei , Madsen Louis A. , Lin Feng
Published: December 2024

Polymer electrolytes hold great promise for safe and high-energy solid-state batteries. Multiphase polymer electrolytes, consisting of mobile and rigid phases, exhibit fast ion conduction and desired mechanical properties. However, fundamental challenges exist in understanding and regulating intricate chemomechanical interactions at the electrode-electrolyte interface, especially when using a high-voltage layered cathode. Here, we report that depletion of the mobile conductive phase at the interface contributes to battery performance degradation. Molecular ionic composite electrolytes, composed of a rigid-rod ionic polymer with small mobile cations and anions, serve as a multiphase platform to investigate the evolution of conductive domains at the interface. Synchrotron chemical and structural analyses enable the direct visualization of concentration polarization and spatially resolve the interfacial chemical states over a statistically significant field of view for buried interfaces. We discover that concentration and chemical heterogeneities prevail at electrode-electrolyte interfaces, leading to interfacial chemomechanical degradation. We further demonstrate an interphase tailoring strategy based on electrolyte additives to mitigate such interfacial heterogeneity and improve battery stability. While polymer electrolytes have been considered "deformable" for conformal interfaces, our work shows the hidden roles of interfacial chemomechanics in polymer electrolytes and provides an effective mitigation approach.

Figure 1
Chalcogenide-Based Gels As High-Capacity Electrodes for Lithium-ion Batteries
Authors: Islam Saiful M. , Taohedul Islam , Weret Misganaw , Roy Subrata , Bayat Sahar , Rao Keerthan , Li Mengya , Risko Chad M. , Wiaderek Kamila , Amin Ruhul
Published: December 2024

Chalcogenide-based (aero)gel, also known as chalcogel, represents a distinct category of porous, nanoaggregated materials characterized by their highly disordered and amorphous structure. The predominant structural feature within chalcogel nanoparticles is the presence of a polysulfide backbone, which can mimic a sulfur equivalent electrode material for Li-ion sulfide batteries. This work endeavors to expand explore chalcogel’s applications in developing high-energy-density materials as conversion-based sulfur equivalents electrodes for lithium-ion batteries. We have also pioneered the synthesis of a novel class of materials called "chalcocarbogels," which have demonstrated exceptional specific capacity and cyclic stability in both Li-ion and Na-ion batteries. Our work underscores the promising prospects of chalcogenide-based aerogels in advancing energy storage technologies and addressing environmental challenges.
Safety of Lithium-Ion Batteries with Regard to Film Forming Additives Vinylene Carbonate and Fluoroethylene Carbonate
Authors: Geuder Karsten , Seifert Hans Jürgen , Ziebert Carlos
Published: December 2024

Ensuring the safety of lithium-ion batteries is paramount given their widespread applications and the potential risk of fire and explosion. To improve our understanding of thermal runaway behavior, we conducted in-depth research focusing on the electrolyte and two commonly used film forming additives, vinylene carbonate (VC) and fluoroethylene carbonate (FEC).

Dry cells were filled with a control electrolyte (EC:EMC, 3:7 wt%, 1M LiPF6). In addition, 5 wt% of either VC or FEC was added to the electrolyte. After formation, the cells were subjected to 10 initial cycles and a characterization test, consisting of a capacity check and a pulse test for the determination of the internal resistance. The negative electrode is graphite and the positive electrode is LiNi0.6Mn0.2Co0.2O2 (NMC622). All cells showed a stable capacity of more than 1 Ah. After the characterization test, the electrodes and separator were extracted from some cells in an argon-filled glove box (H2O and O2 < 0.1 ppm) for further analysis. The thermal behavior of the individual electrodes in combination with the electrolyte was measured using highly sensitive Tian-Calvet calorimeters (Setaram) in the temperature range of 30 to 300°C. Safety testing on the full cells was performed using the Heat-Wait-Seek (HWS) method with fully charged cells (SoC100) inside an ES-ARC (Thermal Hazard Technologies).

VC and FEC additives decompose before ethylene carbonate (EC) from the electrolyte during initial charging, as evidenced by peaks in the differential capacity analysis at voltages of 2.4 V and 2.6 V, respectively. Conversely, decomposition without additives begins just before 2.8 V. VC and FEC are used to create a more stable solid electrolyte interface (SEI) at the anode. The thermal stability of the separator was tested with a Differential Scanning Calorimeter DSC204 (Netzsch). The melting of the separator started at 119°C, which is typical for polymer separators used in lithium-ion batteries.

In the HWS test, the cells are heated in 5°C increments inside the Accelerating Rate Calorimeter (ARC), followed by a waiting period to ensure thermal equilibrium. The ARC then looks for self-heating of the battery. When a threshold of 0.02°C/min is reached, the ARC switches to a quasi-adiabatic mode and tracks the temperature of the cell. During thermal abuse, cells without additives showed an earlier onset of exothermic reactions, with thermal runaway observed in all cells tested between 195°C and 205°C.

A thorough understanding of thermal runaway is critical to the safety of lithium-ion batteries. An accurate understanding of the electrolyte composition provides a deeper insight into its safety implications. Future research will further investigate the effects of aged cells with the same electrolyte combinations.
LiNiO2 Mechanical and Phase Stability Improvements at Deep Charge Predicted by Pillaring
Authors: Bergschneider Matthew , Kong Fantai , Hwang Taesoon , Cho Kyeongjae
Published: December 2024

Increasing energy density of Li-ion layered cathode materials will require access to deep charge states of high-nickel NCM/NCA and LiNiO2, predicated by overcoming numerous issues. In liquid electrolyte systems, the strain following anisotropic volumetric strain at the deep charge state induces separation of secondary particles and crack formation in primary particles, revealing greater surface area and exacerbating interfacial instabilities and pulverizing the cathode active material.[1] This anisotropic strain must also be arrested to mitigate delamination of solid-solid interfaces with solid-state electrolytes, thus enabling next-generation battery technology via “zero-strain” cathodes.[2] Density functional theory calculations evaluated the structural evolution throughout delithiation of Li1-xNiO2 (x = 0 → 1), highlighting the monoclinic structure and H2-H3 phases at deep charge.[3] The Li-interlayer contribution to the lattice collapse and mechanical stiffness is found to be highly correlated, and so interlayer cation concentration strongly influences mechanical property and phase stability. Detailed analysis of the local electronic environment for LixNiO2 contrasted the impact of delithiation, cation mixing, and dopants — both pillaring and transition metal substitutive. Modeling of select Li-interlayer pillaring dopants show improvements across the full range of delithiation with lessened volumetric change and more consistent mechanical stiffness trends by compensating anion electron density in the interlayer.

[1] H.-H. Ryu, K.-J. Park, C. S. Yoon, Y.-K. Sun, Chem. Mater 2018, 30, 1155

[2] R. Zhang, C. Whang, P. Zou, R. Lin, L. Ma, L. Yin, T. Li, W. Xu, H. Jia, Q. Li, S. Sainio, K. Kisslinger, S. E. Trask, S. N. Ehrlich, Y. Yang, A. M. Kiss, M. Ge, B. J. Polzin, S. J. Lee, W. Xu, Y. Ren, H. L. Xin, Nature 2022, 610, 67-73

[3] M. Mock, M. Bianchini, F. Fauth, K. Able, S. Sicolo, J. Mater. Chem. A 2021, 9, 14928
Tactical Enhancement in the Cycle Stability of LiCoO2 at 4.6 V Via Synergetic Al-Mg-F Doping
Authors: Park Sangbin , Seok Jangwhan , Lee Wontae , Lee Seongeun , Yoon Won-Sub
Published: December 2024

Uplifting the charging voltage of LiCoO2 is vital for advancing beyond the current energy density thresholds in lithium-ion batteries. However, the structural instability of LiCoO2 in the deep delithiated state challenges the practical adoption of high-voltage LiCoO2. Herein, we attained enhanced stability of both the crystal and electronic structures of LiCoO2 at 4.6 V (vs. Li/Li+) through targeted doping of Al, Mg, and F at three distinct lattice sites. Al and Mg work together to inhibit or delay phase transitions, ensuring the crystal structure remains uncollapsed even with the appearance of the detrimental H1-3 phase. Moreover, all elements, especially F, prevent oxygen oxidation during charging and ensure the tight bonding of surface oxygen to the lattice. These enhancements allow the particles to remain undamaged through numerous cycles, without cracks or dense surface reduction layers, thereby maintaining a wide charge/discharge range. Therefore, the tri-site modification strategy is effective in minimizing capacity sacrifice and boosting battery performance, with every dopant function in a synergistic way.

Figure 1
CNT/GO Zinc Composite as Dual-Functional Electroconductive and Lithophilic Coatings for Cu-Current Collectors in Anode-Free Li Batteries
Authors: Afzali Pooria , Magagnin Luca
Published: December 2024

The novel concept of anode-free lithium batteries (AFLBs), which eliminate excess lithium while preserving numerous advantages, presents certain challenges such as notable capacity loss, low electronic conductivity, and reduced coulombic efficiency. To address these issues, modified lithiophilic current collectors are essential for enhancing electrochemical performance. This study focuses on surface modification of the copper current collector through carbonaceous zinc composites co-electrodeposition benefiting lithiophilicity and electroconductivity [1]. These composites, including 1D Zn/Carbon Nanotubes (CNT-Zn) and 2D Zn/Graphene Oxide (GO-Zn), are coated on the copper current collector, varying their compositions to create a lithiophilic thin layer and improve electroconductivity [2-3]. The aim of this modification is to promote smoother plating and stripping processes, thereby facilitating uniform lithium deposition without dendrite formation. The composite-modified current collector demonstrated improved cyclability over 200 cycles at 0.393 mA, reduced overpotential at various applied current densities (ranging from 0.392 to 1.962 mA cm-2), and provided uniform lithium deposition. Electrochemical Impedance Spectroscopy (EIS) revealed the most reduced charge transfer resistance (Rct) of 38.4 Ω for Zn/Graphene Oxide (GO-Zn) after the first cycle. It also indicated that a higher amount of CNT and GO leads to worse electrochemical performance due to the agglomeration of carbonaceous particles on the substrate.

References

Pooria Afzali, Eugenio Gibertini, Luca Magagnin, Improved plating/stripping in anode-free lithium metal batteries through electrodeposition of lithiophilic zinc thin films,, Electrochimica Acta, Volume 488,2024,144190, ISSN 0013-4686, https://doi.org/10.1016/j.electacta.2024.144190.

Ge J, Hong J, Liu T, Wang Y. Rational design of a self-supporting skeleton decorated with dual lithiophilic Sn-containing and Ndoped carbon tubes for dendrite-free lithium metal anodes. J Mater Chem A 2022;10:11458-69.

Mehmet Oguz Guler, Tugrul Cetinkaya, Ubeyd Tocoglu, Hatem Akbulut, Electrochemical performance of MWCNT reinforced ZnO anodes for Li-ion batteries, Microelectronic Engineering, Volume 118, 2014, Pages 54-60, ISSN 0167-9317, https://doi.org/10.1016/j.mee.2013.12.029
Unraveling the Sequential Effect of Dual-Layered Hybrid Graphite Anodes on Electrode Utilization during Fast-Charging Li-Ion Batteries
Authors: Kang Jiwoong , Lim Jaejin , Lee Hyuntae , Chae Sujong , Lee Yong Min , Lim Minhong
Published: December 2024

The efficient and fast recharging of Li-ion batteries without compromising capacity or safety is paramount in advancing energy storage technologies. This study addresses this challenge by developing a novel electrode design known as dual-layer electrode (DLE) technology, achieved via a carefully orchestrated sequential coating process involving two distinct anode materials. The primary objective is to minimize cell polarization, a critical factor impacting charging efficiency and battery longevity, particularly at higher charging currents.

The research employs advanced electrochemical techniques such as electrochemical impedance spectroscopy (EIS) and distribution of relaxation times (DRT) analysis to delve into the dynamic evolution of electrode impedances. Notably, synthetic graphite (SG) exhibits varying impedance characteristics with changes in the state of charge (SOC), contrasting with the relatively stable impedance observed in natural graphite (NG) across SOC variations. This fundamental difference is a critical determinant in arranging NG and SG layers within the DLE, strategically considering the temporal SOC gradient encountered during fast charging cycles.

The study leverages simulation models alongside experimental validation to ascertain the optimal positioning of NG and SG layers within the DLE structure. The results demonstrate that placing NG atop SG in the DLE configuration significantly reduces overall resistance, leading to remarkable performance gains. Specifically, the DLE exhibits a remarkable 61.0% capacity retention over 200 cycles when charged at a 4 C rate (equivalent to a 15-minute charging duration). This performance surpasses counterparts with reversed sequential coating and even outperforms single-layer electrodes utilizing either NG or NG/SG mixed electrodes.

Furthermore, this research contributes valuable insights into the combinatorial sequence for multi-layer coating of various active materials, particularly in thick-electrode designs. The findings hold significant implications for advancing the development of high-performance Li-ion batteries tailored for fast-charging applications across diverse sectors by achieving lower resistivity and enhanced charging efficiency.
Improving Cycling Performance of Anode-Free Lithium Battery Via Stabilizing Lithium Deposition Under Protection Layer
Authors: Lim Hyung-Seok , Kim Un Hyuck , Cao Xia , Zhang Ji-Guang
Published: December 2024

High voltage anode-free lithium batteries (AFLBs) hold great potential for achieving superior energy density compared to the conventional batteries. However, ensuring a prolonged cycle life for AFLBs remains a significant challenge due to persistent side reactions between the lithium deposited on the anode current collector and the electrolyte. To address this issue, a protective layer for the deposited lithium on the current collector is critical to stabilize the interface and minimize the electrolyte/lithium consumption for long-term cell operation. We developed an unique lithium protection layer (LPL) to float up and down during Li depositing and stripping on the current collector. One of the key advantages of our LPL design is its ability to promote the formation of a stable solid electrolyte interface (SEI) predominantly on the top surface of the LPL, enabling a bottom deposition of Li under the protection layer and minimizing the exposure of the deposited Li to electrolyte. This strategy enhances the protective effect on the deposited lithium from electrolyte corrosion. We demonstrated that the uniform SEI layer formed on top of LPL and minimized electrolyte/lithium consumption significantly enhance the cycle life of AFLB coin cells operated with high loading (areal capacity of 4 mAh cm-2) cathodes.
Non-Dendritic Lithium Plating Enabled By LiBF4 and Lidfob Salts Prevents Rollover Failiure in High-Voltage Li Ion Batteries
Authors: Arifiadi Anindityo , Wichmann Lennart , Demelash Feleke Berehane , Brake Tobias , Buchmann Julius , Lechtenfeld Christian , Yan Peng , Wiemers-Meyer Simon , Winter Martin , Kasnatscheew Johannes
Published: December 2024

Increasing the upper cut-off voltage (UCV) offers a pragmatic way to enhance energy density of Li ion batteries (LIBs). Nevertheless, it is accompanied by rapid capacity fade, and in the worst case, by a rollover failure. Rollover failure originates from high surface area lithium (HSAL) formation and subsequently, active lithium losses (ALL), which is triggered by transition metal deposits (TM) on the negative electrode in the course of electrode crosstalk. The electrolyte is capable to alter this failure cascade, either via suppressing TM dissolution and/or scavenging dissolved TMs. While the effect of solvents, additives, and LiPF6 decomposition products have been investigated, the impact of lithium salts on the performance of high-voltage LIBs, parricularly in practical cell format, remains ambiguous.

In this work, the performance of common lithium salts, particularly LiBF4 and lithium difluoro oxalatoborate (LiDFOB), in an ethylene carbonate (EC)/ethyl methyl carbonate (EMC) mixture, are investigated in NCM 622 || graphite wounded pouch cells. Though the lower oxidative stability of LiBF4 and lithium difluoro(oxalate)borate (LiDFOB) compared to LiPF6 increases TM dissolution, they enhance capacity retention compared to LiPF6. Capacity endpoint slippage, combined with scanning electron microscopy and nuclear magnetic resonsnce analyses reveals that these salts suppress ALL due to the formation of non-dendritic metallic lithium over the course of TM-induced lithium plating. Also, active lithium generation enabled by DFOB- anion oxidation on the positive electrode, can additionally compensate ALL until the DFOB- anion is fully consumed. Consequnetly, lithium morphology is suggested to be more decisive than dissolved TM amounts in causing rollover failure, pointing to the importance of Li salt design for optimizing high-voltage electrolytes.
Advanced Analysis of Binder Distribution within Multilayer Composite Electrodes of Lithium Ion Batteries
Authors: Bak Cheol , Kim Kyung-Geun , Lee Hyuntae , Roh Youngjoon , Dzakpasu Cyril Bubu Bubu , Lim Jaejin , Lee Hyobin , Lee Hongkyung , Lee Yong Min
Published: December 2024

The loading levels of composite electrodes are increasing continuously to satisfy the energy density requirements of lithium-ion batteries (LIBs) in electric vehicles (EVs). Furthermore, a faster coating and drying process in the mass-production line yields a nonuniform binder distribution. Thus, it is necessary to understand its distribution within the composite electrode and control it for a better and more reliable electrochemical performance. Therefore, we propose the utilization of an advanced multilayer electrode model consisting of several electrode layers with different binder contents. Using these controlled electrode models, the adhesive strength within each layer was examined using a surface and interfacial cutting analysis system (SAICAS). This was followed by a composition analysis using EDX on each surface. Subsequently, the electronic conductivities of the model electrodes were measured using an electrode resistance meter to determine the bulk and interfacial electrode resistances. Furthermore, the electrochemical properties of each model electrode were evaluated to correlate their relationships and design the optimum binder distribution. Thus, this multilayer model provides a highly effective platform for determining the optimum binder distribution in highly loaded composite electrodes for high-energy–density and long-lasting LIBs.
(Invited) Development and New Perspectives in Lithium Ion Conductors and Solid-State Batteries
Authors: Kanno Ryoji , Hori Satoshi , Shimizu Keisuke , HIkima Kazuhiro
Published: December 2024

All-solid-state batteries, which consist entirely of solid components, are being developed as the energy storage devices for the next generation. In the presentation, after showing the history, current status, and challenges of solid-state battery development, our research on the solid-state electrolyte exploration and solid-state battery development will be presented. We investigated the solid electrolytes to improve the performance of solid-state batteries, and the battery reactions using model-type solid-state batteries.

We have explored new solid electrolytes and found a material Li10GeP2S12(LGPS) with conductivity comparable to or higher than the ionic conductivity of Li-based organic solvent electrolytes. It was found that the power density of batteries can be dramatically increased by utilizing the solid-electrolytes of superior ionic conductivity. Based on the LGPS material developments, the intrinsic advantages of the solid-state battery, fast ion diffusion mechanism in the LGPS solids, and challenges of developing the technology needed to produce practical batteries will be discussed.

We have developed model battery system based on the idea that battery reactions can be observed more in detail when batteries are solid-state. Battery reactions proceed at the electrode/electrolyte interface. It is not well understood how the electrochemical reactions at the interface and the changes in the electronic structure of the electrode proceed during charging and discharging. In solid-state batteries, the electrode-electrolyte interface can be considered as a heterojunction interface in semiconductors. Spectroscopic methods can reveal the electronic structure of the battery during charge-discharge reactions.

As solid-state batteries become practical devices, the battery science and technology will also progress.
All-Solid-State Lithium–Sulfur Batteries Enabled By Single-Ion Conducting Particle Electrolytes
Authors: Park MoonJeong
Published: December 2024

The demand for safer alternatives to liquid electrolytes in lithium-ion batteries has stimulated the development of all-solid-state lithium batteries. These advanced batteries aim to mitigate potential hazards associated with flammability and dendrite formation during operation. Additionally, the integration of solid-state electrolytes creates opportunities to improve the energy and power densities of lithium batteries by enabling the direct utilization of lithium metal as the anode. In this study, we designed solid-state hybrid electrolytes with single-ion conducting properties by co-assembling binary polymer nanoparticles with large surface areas and excellent thermodynamic compatibility. These electrolytes were developed by synthesizing two distinct types of core–shell polymer nanoparticles with mechanically robust cores and shells capable of facilitating Li+ transport. By controlling the nanoparticle size and number, we created superlattices that optimized the Li+ concentration and transport. The electrolytes exhibited a remarkable ionic conductivity (10-4 S cm-1), lithium transference number (0.94), electrochemical stability (up to 6 V), and modulus (0.12 GPa) at 25 °C. The mechanical strength of these electrolytes depended minimally on temperature at 25–150 °C because of the robustness of the cores. These results unequivocally establish the remarkable superiority of the BNPs electrolyte, which avoid the conventional trade-off between conductivity and mechanical strength through the unique design of superlattice structures, thereby representing a significant breakthrough in the field of solid-state single-ion electrolytes. When implemented in Li–S batteries with no liquids, they demonstrated a stable discharge capacity exceeding 1008 mAh g-1, a cycle life of over 200 cycles, and a rate capability with a discharge capacity of 627 mAh g-1 at 3C. Our findings will pave the way for the safe operation of future high-energy-density lithium batteries utilizing solid-state hybrid electrolytes.

Figure 1
Degradation Mechanism of Phosphate-Based Li-Nasicon Conductors in Alkaline Environment
Authors: Lam Benjamin X. , Li Zhuohan , Ceder Gerbrand
Published: December 2024

Li-NASICON solid-state superionic conductors have traditionally been regarded as promising candidates for Li-air applications because of their stability in ambient air and water [1], [2]. However, the presence of water in the cathode can change the discharge product from Li2O2 to LiOH [3], [4], inducing a highly alkaline environment which may degrade cathode and separator materials. Here, we investigate the impact of octahedral substitution on the alkaline stability of common Li-NASICON chemistries through a systematic experimental case study of LiTixGe2-x(PO4)3 (LTGP) with varying x = 0 - 2.0. Density functional theory calculations are combined to gain mechanistic understandings of the alkaline instability. We demonstrated that the alkaline instability of LTGP is mainly driven by the dissolution of PO4 polyanion groups, which subsequently precipitate as Li3PO4. The introduction of Ti facilitates the formation of a Ti-rich compound on the surface that eventually passivates the material, but only after significant bulk degradation. Consequently, phosphate-based Li-NASICON materials exhibit limited alkaline stability, raising concerns of their viability in humid Li-air batteries.

[1] N. Imanishi, S. Hasegawa, T. Zhang, A. Hirano, Y. Takeda, and O. Yamamoto, “Lithium anode for lithium-air secondary batteries,” Journal of Power Sources, vol. 185, no. 2, pp. 1392–1397, Dec. 2008, doi: 10.1016/j.jpowsour.2008.07.080.

[2] R. Chen, Q. Li, X. Yu, L. Chen, and H. Li, “Approaching Practically Accessible Solid-State Batteries: Stability Issues Related to Solid Electrolytes and Interfaces,” Chem. Rev., vol. 120, no. 14, pp. 6820–6877, Jul. 2020, doi: 10.1021/acs.chemrev.9b00268.

[3] S. Ma, J. Wang, J. Huang, Z. Zhou, and Z. Peng, “Unveiling the Complex Effects of H2O on Discharge–Recharge Behaviors of Aprotic Lithium–O2 Batteries,” J. Phys. Chem. Lett., vol. 9, no. 12, pp. 3333–3339, Jun. 2018, doi: 10.1021/acs.jpclett.8b01333.

[4] T. Liu et al., “Cycling Li-O2 batteries via LiOH formation and decomposition,” Science, vol. 350, no. 6260, pp. 530–533, Oct. 2015, doi: 10.1126/science.aac7730.
Advancing Li-Transport in Composite Polymer Electrolytes with Functionalized LLZO Nanoparticles
Authors: Tepavcevic Sanja , Counihan Michael , Lee Jungkuk , Mirmira Priyadarshini , Barai Pallab , Burns Meghan , Amanchukwu Chibueze , Srinivasan Venkat , Zhang Yuepeng
Published: December 2024

The combination of Li+-conducting ceramics and polymers offers a new pathway to create better electrolytes for solid state batteries with both high ionic conductivity and good (electro)mechanical interfacial properties. Achieving synergy in Li transport between ion-conducting ceramic and polymer in a composite electrolyte has been proven to be difficult. The total Li-ion conductivity of the composite polymer electrolytes is still governed by the polymer matrix due to high interfacial resistance between the garnet particles and the PEO/LiTFSI matrix. We modeled our composite electrolytes with two Li+-conductive phases (PEO and LLZO) and two interphases. The conductive interphase is attributed to the LLZO nanofiller’s disruption of PEO crystallization, essentially acting as a plasticizer. The resistive interphase is attributed to the adsorption of PEO on LLZO and the limited segmental motion of the polymer chains when near the LLZO surface. To disrupt this resistive interphase at ceramic/polymer interface we synthetically modified the surface of LLZO nanoparticles with functional silane chemistries (Figure 1). This simultaneously added surface moieties that interact with the polymer matrix and protected the LLZO surface from continual Li2CO3 formation. The incorporation of functionalized nanoparticles into the composite polymer membrane resulted in lower interfacial impedance, improved conductivity and transference numbers and the cycling characteristics against the lithium anode in addition to significantly improved handleability and processability. 6,7Li solid-state NMR shed the light on the mechanism of enhanced Li-transport and the nature of the resistive interphase. This work revealed a new design strategy for a composite polymer electrolyte with enhanced Li+- transport properties for high-performance Li metal batteries.

Figure 1
Hydrothermal Synthesis of Oxide Solid Electrolyte Nanocrystals with Controlled Shapes for Orientated Ceramics
Authors: Itasaka Hiroki , Mimura Ken-ichi , Liu Zheng , Hamao Naoki , Hamamoto Koichi
Published: December 2024

Oxide solid electrolyte for all-solid-state lithium-ion batteries have advantages over sulfide solid electrolytes in terms of thermal and mechanical stability, safety, and ease of handling. However, high sintering temperatures required to fabricate oxide solid electrolyte ceramics are on obstacle to integration with cathodes and anodes. We recently reported synthesis of lithium lanthanum titanate (LLTO)-based solid electrolyte nanoplates by a hydrothermal method[1]. The hydrothermally synthesized nanoplates could be sintered at a lower temperature than particles synthesized by the solid phase method. It was revealed that the lower sintering temperature was due to the face-to-face stacking of the nanoplates formed through uniaxial molding, which indicated that sintering behvior of oxide solid electrolytes could be controlled by the shape and stacking structure of nanocrystals.

Here, we have synthesized various shaped LLTO-based nanocrystals by changing a Ti source in the hydrothermal method to investigate dependence of sintering behavior on the shape of the nanocrystals and have investigated Li ion conductivity of the ceramics fabricated from the nanocrystals. For synthesis of LLTO-based nanocrystals, we newly introduced two types of titanium sources: anatase-type and rutile-type TiO2, in addition to titanium(IV) bis(ammonium lactate) dihydroxide (TALH), which was used for the synthesis of the nanoplate in the previous report. Scanning electron microscopy observation showed that anatase-type TiO2 yielded a mixture of nanocubes and nanorods and rutile-type TiO2 yielded nanosheets. Scanning transmission electron microscopy observation and electron energy loss spectroscopy confirmed that the nanocrystals yielded from anatase- and rutile-type TiO2 had the LLTO-based perovskite crystal structure as the nanoplates yielded from TALH. Comparison of the sintering behavior at 1000°C for these different shaped nanocrystals subjected to uniaxial molding revealed that the nanocrystals with high aspect ratio (nanoplate, nanorod, and nanosheet) sintered more easily than the nanocubes and the ceramics of the nanoplates and nanosheets had {100} and {110} orientation, respectively. These oriented ceramics showed ionic conductivity according to the crystallographic orientations. The present result can provide an insight into controlling ionic conductive direction in oxide solid electrolyte ceramics by using shape-controlled nanocrystals.

Acknowledgement

This study was supported by a project (No. JPNP20005), commissioned by the New Energy and Industrial Technology Development Organization (NEDO), Japan.

Reference

[1] K. Mimura, N. Hamao, H. Itasaka, Z. Liu, K. Hamamoto, J. Sol-Gel Sci. Tech. 104, 599 (2022).
Microstructure of Electrodeposited Al in an AlCl3/Urea Electrolyte for Rechargeable Al Batteries
Authors: Jian Ming-Si , Lin Meng-Chang , Chu Peng-Wei
Published: December 2024

Owing to the natural abundance, low cost, low flammability, and high theoretical volumetric capacity (8,046 mAh/cm3) of aluminum (Al), rechargeable Al batteries with Al metal anodes have emerged as one of the promising candidates for future energy storage systems. Most studies in the literature focus on the development of novel cathode materials and their capabilities to store Al or Al-containing ions to support the charge/discharge cycles, while the plating/stripping behavior and microstructure evolution of the Al metal anodes are relatively less studied. Therefore, in this research, electrodeposition of Al was performed in an AlCl3/urea ionic liquid analog electrolyte [1,2], and the microstructure of the electrodeposited Al was characterized by scanning electron microscope (SEM) and other microstructure characterization techniques. The prepared AlCl3/urea electrolyte showed a reversibility of >99% to support reversible Al plating and stripping. The electrodeposited Al showed a granular structure with a grain size of 3.06±0.80 μm when deposited at 2.25 mA/cm2 for 40 minutes on the pure Al anode. The dependence of the morphology and crystal orientation of the electrodeposited Al on the deposition parameters, including current density, deposition time, and substrate materials, will be discussed based on the microstructure characterizations.

[1] H.D. Jiao et al., A Rechargeable Al-ion Battery: Al/Molten AlCl3-Urea/Graphite, Chemical Communications, vol. 53, pp. 2331-2334, 2017.

[2] Y.H. Bian et al., Using an AlCl3/Urea Ionic Liquid Analog Electrolyte for Improving the Lifetime of Aluminum-Sulfur Batteries, ChemElectroChem, vol. 5, pp. 3607-3611, 2018.

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Pathogenic Factor Analysis of Shoulder Periarthritis and Design of Virtual Reality Exercise Intervention System
Authors: Tian Yucheng , Qiu Dan , Song Renjie , Cheng Xue , Chen Feiyu , Sun Dongqing , Zhou Yiduo , Cai Shaomin , Wang Zhaowei , Zhang Weijia
Published: December 2024

Shoulder periarthritis, a prevalent musculoskeletal disorder, causes significant pain and functional impairment, severely affecting patients’ quality of life. With the increasing incidence of shoulder periarthritis linked to modern lifestyle changes, effective prevention and treatment strategies remain elusive. This study explores two areas: first, identifying risk factors for shoulder periarthritis through Mendelian randomization (MR) analysis, and second, designing a motion intervention system incorporating MediaPipe and virtual reality (VR) technology. The MR analysis revealed positive causal relationships between shoulder periarthritis and body mass index (BMI), cigarettes per day, insomnia, and sedentary behavior, while higher educational attainment was inversely associated with the condition. Based on these findings, we developed a “VR Harvest” exercise system aimed at alleviating shoulder stiffness due to prolonged sitting and reducing shoulder pain. By adjusting task difficulty to increase physical activity, the system also facilitates BMI reduction, potentially lowering the risk of shoulder periarthritis. The experimental results indicate that the “VR Harvest” therapy effectively alleviates pain and, compared to traditional exercise therapy, offers greater enjoyment, thereby enhancing participant engagement. Moreover, participants across different BMI categories experienced reductions in BMI after completing the intervention. This study offers a novel approach for shoulder periarthritis prevention and treatment, leveraging VR technology to improve both symptom relief and underlying risk factors.
ISM‐BN‐Based Schedule Risk Analysis in Large‐Scale Public Projects
Authors: Chen Yuan , Li Yuening , Zha Yachuang
Published: December 2024

Large‐scale complex public projects face greater, more uncertain, and more diverse risks due to their particular characteristics of large size, long duration, and complexity, which bring both opportunities and challenges for construction enterprises. At present, the research on the schedule risk of large‐scale public projects mainly focuses on identifying risk factors causing schedule delays and predicting such delays. However, there is a lack of comprehensive analysis of the interactions among risk factors, and quantitative assessments of the impact intensity and combined effects among these factors are not conducted. Additionally, the use of Bayesian networks (BNs) for quantitative risk assessments faces challenges such as unclear causal and dependency relationships among factors in complex systems and insufficient model interpretability. The purpose of this study is to introduce interpretive structural modeling (ISM) to analyze the relationships among risk factors at various levels, thereby facilitating the construction of a BN for predicting delay risks in large‐scale and complex public projects. This approach aims to effectively address the prevalent issues of incompleteness and uncertainty inherent in such projects. Furthermore, based on this foundation, the study delves into the quantitative relationships and integrated effects among risk factors. Initially, a comprehensive methodology is employed to establish a comprehensive set of schedule risk factors. Subsequently, ISM is utilized to analyze the hierarchical relationships among these factors, which in turn supports the modeling of a BN to construct a schedule delay risk assessment model. This model enables the prediction and quantification of schedule risks, which are then validated through real‐world project cases. Finally, a thorough examination of quantitative relationships, such as factor importance, sensitivity, and integrated effects, is conducted. The results demonstrate that the established model exhibits high accuracy, reusability, enhanced interpretability, and credibility, significantly improving the prediction of schedule delays in practical engineering projects. Moreover, it clarifies the quantitative relationships among the risk factors contributing to schedule delays, providing a scientific and effective theoretical basis and control tool for schedule risk management.
Variability in Notification of Positive Newborn Screening Results for Sickle Cell Trait Across the United States
Authors: Scott Jayla Lynn , Christian Jana , Plazas Montana Manuela , Miller Yvette M. , Naik Rakhi P.
Published: December 2024

Universal in the United States (US) since 2006, newborn screening (NBS) programs for sickle cell disease (SCD) allow for early identification of the disease and, as an unintentional byproduct, identification of sickle cell trait (SCT). Unlike other carrier states, SCT is highly prevalent and is found in nearly 3 million Americans, which results in important reproductive implications. Currently, all NBS programs in the US are responsible for their own policies regarding SCT notification, and little is known about how SCT notification practices are performed and how these practices vary across NBS programs. We surveyed NBS programs personnel in all 50 states, the District of Columbia, and the US’ territories of Puerto Rico and Guam (n = 53) using an electronic survey. There was a 100% response rate. All NBS programs (100%) provide notification of SCT status to either a pediatrician or parent: 49% notify the pediatrician only, 45% notify both the pediatrician and parent, and 6% notify the parent only. A total of 98% of NBS programs retain electronic records of SCT status, but only 38% can be directly accessed by pediatricians/primary care doctors. No state operates a publicly available database that allows individuals to access their own records. Only one state provides renotification at reproductive age. In conclusion, there is wide variability in NBS practices for SCT notification. This study demonstrates a need for national guidelines to standardize SCT notification across the US to ensure effective notification and counseling for SCT.
Overweight and Obesity Among People Living With HIV on Dolutegravir‐ and Efavirenz‐Based Therapies: A Comparative Cross‐Sectional Study
Authors: Jemal Mohammed , Adugna Adane , Getinet Mamaru , Baylie Temesgen , Waritu Nuredin Chura
Published: December 2024

Background: Overweight and obesity have arisen as major public health challenges, affecting not just the general population but also people living with human immunodeficiency virus (HIV) (PLWH). Obesity and being overweight are both risk factors for heart disease and other related complications. However, little is known in our setting. As a result, this study was conducted to evaluate the prevalence of overweight and obesity and its associated factors among PLWH on dolutegravir (DTG)‐ and efavirenz (EFV)‐based therapies.

Methods: An institution‐based comparative cross‐sectional study was carried out from June 30, 2021, to August 30, 2021. We purposively recruited 128 participants who have been on DTG (n = 64)‐ and EFV (n = 64)‐based regimens for ≥ 6 months. Demographic, anthropometric, laboratory, and clinical data were collected using a structured questionnaire. The data were entered into EpiData Version 4.6 and analyzed using SPSS Version 26.0. Multivariable logistic regression was utilized to identify the factors that are associated with being overweight or obese, and the significance level was set at p < 0.05.

Result: The prevalence of overweight and obesity was 28.1% in the DTG‐prescribed participants and 15.6% in the EFV‐prescribed participants. Age ≥ 40 years (adjusted odd ratio (AOR) = 3.86; 95% confidence interval (CI): 1.08–13.73; and p = 0.037), cluster of differentiation 4 (CD4) T‐cell counts ≥ 500 cells/mm3 (AOR = 2.95; 95% CI: 1.01–8.59; and p = 0.029), and insufficient physical activity (AOR = 4.6; 95% CI: 1.53–13.84; and p = 0.007) were predictors of overweight and obesity.

Conclusion: Overweight and obesity are not uncommon among PLWH on ART. While the difference was statistically insignificant, the prevalence of overweight and obesity was higher in patients treated with DTG compared with those treated with EFV. Older age, higher CD4 cell counts, and insufficient physical activity were associated with overweight and obesity. As a result, healthcare providers must understand the health implications of obesity and consider incorporating targeted weight control programs into standard HIV treatment.
Histological Features of Delayed Foreign Body Granuloma With Epithelioid Histiocyte Aggregation and Eosinophilic Reaction due to Hyaluronic Acid Injection
Authors: Nishimura Michiko , Sakamoto Shinnichi , Hoshino Miyako , Miyazaki Yuji , Yamamoto Junichiro , Sakashita Hideaki , Kusama Kaoru , Kikuchi Kentaro
Published: December 2024

Background: Dermal fillers such as hyaluronic acid (HA) have been widely used in recent years as a less surgically invasive cosmetic treatment. Although delayed foreign body granuloma may occur as a rare adverse reaction after the procedure, detailed histological reports are still limited. When occurring on the buccal mucosa of the oral cavity, the histopathology may resemble some lesions of minor salivary gland origin due to the material properties of HA. Here we report a delayed foreign body granuloma associated with HA showing eosinophilic infiltration of the buccal mucosa, with characteristic histological and immunohistological features.

Case Presentation: A 61‐year‐old woman presented with swelling and a burning sensation in the right buccal mucosa. On initial examination, a 25 × 20‐mm mass was palpated on the anterior margin of the right masseter muscle. Examination of a biopsy specimen revealed multiple pseudoduct‐like structures containing mucoid substance within the mucosal lamina propria. The mucoid substance was positively stained with Alcian blue (AB) and surrounded by CD68‐positive epithelioid cells and multinucleated giant cells. Many histiocytes had infiltrated into the surrounding area, and numerous eosinophilic infiltrates were also evident. After a review of the patient’s history, a diagnosis of delayed foreign body granuloma associated with HA injection was made.

Conclusion: We have reported a case of delayed foreign body granuloma with eosinophilic and histiocytic infiltration following injection of HA. It was suggested that the marked eosinophilic infiltration around macrophages was due to not only an allergic reaction, but also in part to increased macrophage aggregation.