bluuebunny/crossref_metadata_2025_split 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.
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
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.
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.
(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.
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.
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.

Figure 1