bluuebunny/crossref_metadata_2025_split huggingface dataset:
(Invited) The Complex Mechanisms That Create High Li-Ion Mobility in Oxides and Sulfides
Authors: Ceder Gerbrand 
Published: November 2022

The exciting development of solids with extremely high Li-ion conductivity, higher than that in traditional liquid electrolytes, in the last decade has forced us to rethink the processes that make cations move in solids. Super-ionic Li conductors typically have very high Li concentration so that their conductivity behavior cannot be explained with simple point defect mechanisms. Instead, ideas of concerted motion or highly correlated motion have been proposed.
I will discuss our current understanding of the mechanisms that provide high Li-ion conductivity. We find that due to the high screening power of S2- Li mobility in sulfides is mostly determined by local anion coordination and its variation along the migration pathway, making anion topology the main determinant of Li-ion conductivity. As a result, we find that there is little coordinated or concerted motion in sulfides. In contrast, due to the lower screening power of oxides and their lower Li-Li distances, Li-ion conductivity is much more determined by the electrostatic interaction with the other cations, setting the stage for possible concerted motion of multiple ions. I will show how this leads to very specific, but precise rules for selecting structures that may accommodate very fast Li-ion motion.
While fast motion of divalent cations is much less likely, I will show computational results that indicate that even super-ionic motion of ions such as Mg2+ and Ca2+ may be possible in the right framework.
Dual Ion Conducting Solid Electrolyte and Electrochemical Protocol for Interface Design
Authors: Amin Ruhul , Dixit Marm , Parejiya Anand , Essehli Rachid , Muralidharan Nitin , Belharouak Ilias 
Published: November 2022

The major challenges for the development of all solid-state batteries (ASSBs), that would be cheaper and can be charged and discharged faster, are stable solid electrolytes and robust interfacial design. We report the dual ion conduction capability of Na-based NASICON type super ion conductor materials using Na1+xMnx/2Zr2-x/2(PO4)3 (NMZP) as a candidate system [1]. This method enables the use of Na-based NASICON material family in both Na as well as Li all solid-state batteries (Figure 1a). The ionic conductivity NZMPs increased as the x value increased and x = 2 showed the highest room temperature conductivities. Crystallographic analysis using neutron diffraction revealed that conductivities observed in these materials are related to the variations in the Na-O bond length and the concentration of mobile sodium content. Using Galvano static plating and stripping tests, we show that these NMZPs boast good cycling stability against both Na and Li metals which also reveals dual ion conduction. Mechanistic investigations through postmortem SEM/EDS and XPS characterizations of the alkali metal and the cycled NMZPs confirm that the Na-Li ion exchange occurs readily in these materials when electrochemically cycled. ASSBs have several interfaces and the interface properties vary depending on the contact condition, energy states, type defects, and chemical/electrochemical stability. ASSB life and performance rely largely on these interfaces since dendrite formation, Li-depleted space-charge layer generation, and spatial variation in interfacial adhesion originate at the interfaces, which leads to battery failure. Stabilizing Li | SE interface is crucial for the development of high-energy-density solid-state batteries. Current approaches in Li metal stabilization employ energy and cost-intensive protocols that have a detrimental impact on the techno-economic feasibility of the ASSBs. This presentation will focus on the facile, electrochemical protocol for improving the interfacial impedance and contact at the Li | Li6.25Al0.25La3Zr2O12 (LALZO) interface. Implementation of a fraction of second short duration high voltage pulse to a poorly formed interface leads to a sustained improvement in contact impedance and lower overpotentials for electrodeposition and electro-dissolution [2] (Figure 1b). This high pulse protocol does not induce the formation of dendrites on the symmetric cells. This electrochemical protocol has direct application in battery formation cycles as well as online management systems for ASSBs.

Reference

[1]. A. Parejiya, R. Essehli, R. Amin, J. Liu, N. Muralidharan, H. M. Meyer, III, D. L. Wood, III, and I. Belharouak, ACS Energy Letters 6 (2021) 429.
[2]. A. Parejiya, R. Amin, M.B. Dixit, R. Essehli, C. Jafta, D.L. Wood, and I. Belharouak., ACS Energy Lett.
6 (2021) 3669.

Figure 1
(Invited) Interfacial Dynamics of Anode-Free Solid-State Batteries
Authors: Dasgupta Neil P. 
Published: November 2022

There is significant interest in solid-state batteries (SSBs) as an alternative to traditional Li-ion batteries, as they can potentially eliminate the flammable liquid electrolyte and enable Li-metal anodes. However, manufacturing of SSBs with Li metal anodes poses a significant challenge, owing to the highly reactive nature of Li metal. Therefore, there has been a recent increase in interest in “anode-free” configurations, where the Li metal anode is formed in situ using the pre-existing inventory in the cathode. In addition to manufacturing considerations, anode-free configurations also enhance energy density compared to batteries with excess Li metal in the anode. However, compared to pre-formed Li metal/solid electrolyte interfaces, the nucleation, growth, and stripping of Li metal in anode-free SSBs has not been widely studied, and poses unique electro-chemo-mechanical phenomena.
To probe the dynamic interfacial evolution of anode-free SSBs, in this study, I will present results using a complimentary set of in situ/operando methodologies. First, I will describe the morphological evolution of Li nucleation and growth at garnet LLZO solid electrolytes, using a newly developed platform for operando 3-D video microscopy [1]. In particular, the influence of mechanical stresses on both the thermodynamic and kinetic properties of Li will be discussed, and unique electrochemical signatures of anode-free plating will described. A mechanistic framework for these electro-chemo-mechanics will be presented, which results in design rules for improving the homogeneity of Li plating during anode formation.
To compliment this morphological information, I will also present results using operando x-ray photoelectron spectroscopy (XPS) on sulfide solid electrolytes. This allows for direct observation of SEI formation during in situ anode formation. In particular, we observe a transition in reaction pathways from SEI formation to nucleation of Li metal, which is a function of both the charging protocol and the presence of interlayer coatings [2-3]. Finally, these results will be compared and contrasted to anode-free Li plating in liquid electrolytes, and a discussion will be presented on how to optimize plating morphology and reversibility.
[1] E. Kazyak, M. Wang, K. Lee, S. Yadavalli, A. J. Sanchez, M. D. Thouless, J. Sakamoto, N. P. Dasgupta, Submitted (2022).
[2] A. L. Davis, R. Garcia-Mendez, K. N. Wood, E. Kazyak, K.-H. Chen, G. Teeter, J. Sakamoto, N. P. Dasgupta,
J. Mater. Chem. A
8, 6291 (2020).
[3] A. L. Davis, E. Kazyak, D. W. Liao, K. N. Wood, N. P. Dasgupta, J. Electrochem. Soc.
168, 070557 (2021).
Rapid Screening of Novel Electrolytes for High Calendar Lifetime Lithium-Ion Cells with Silicon-Based Anodes
Authors: Verma Ankit , Colclasure Andrew M. , Turczynski Andrew , Trask Stephen E. , Pupek Krzysztof , Abraham Daniel P. 
Published: November 2022

While cycle-life parity between graphite and silicon (Si) based lithium-ion batteries (LIBs) is being reached, calendar lifetime of Si anodes remains disappointing compared to its graphite counterpart1. Silicon anode, owing to its intrinsic high (electro)chemical reactivity, exhibits poorly passivating solid electrolyte interphase (SEI) characteristics in common electrolyte formulations optimized for graphitic systems like LiPF6 salt in EC:EMC solvents. Rapid electrolyte screening for calendar lifetime optimization is essential for enabling silicon anodes, as standardized calendar lifetime estimation with the USABC open circuit voltage reference performance test (OCV-RPT) requires long-duration experiments (~years) for accuracy2. In this work, we perform calendar lifetime screening of novel electrolytes for Si anodes utilizing voltage-hold (V-hold) experiments. The V-hold protocol with shortened runtime (~weeks) affords faster testing as compared to the conventional OCV-RPT protocol. Composite silicon anodes with low (15 wt.% Si) and high contents of silicon (70 wt. %Si) are tested with fluorine-free electrolyte systems (e.g. LiBOB in EC:EMC) and EC free electrolytes (e.g. LiPF6 in FEC:EMC) respectively. Capacity during the V-hold has reversible anode lithiation and irreversible SEI growth contributions; consequently, a physics-based capacity deconvolution algorithm is devised to accurately split the parasitic currents for quantitative calendar lifetime estimation. The development of this synergistic experiment-modeling testing paradigm aids in the identification of electrolyte compositions that form stable, passivating SEI films on the silicon-based anodes.
Figure 1 shows the voltage-hold cycle data for (a) fluorine-free and (b) fluorine-rich (right) electrolytes with 15% Si composite anodes collected in a 3-electrode cell. The corresponding normalized capacity and current profiles for 4.1V hold portion are shown in (c) and (d) respectively. Accurate deconvolution of irreversible capacity from the hold capacity is needed to obtain SEI stability information for calendar lifetime.

1McBrayer, J.D., Rodrigues, M.T.F., Schulze, M.C., Abraham, D.P., Apblett, C.A., Bloom, I., Carroll, G.M., Colclasure, A.M., Fang, C., Harrison, K.L. and Liu, G., 2021. Calendar aging of silicon-containing batteries. Nature Energy, 6(9), pp.866-872.

2U.S. Department of Energy Vehicle Technologies Program, United States Advanced Battery Consortium Battery Test Manual For Electric Vehicles, Revision 3.1, October 2020 http://www.uscar.org/guest/article_view.php?articles_id=86

Figure 1
Decoding the Ceramics Influence in the Composite Electrolytes
Authors: Chavan Kanchan , Barai Pallab , Kim Hong-Keun , Srinivasan Venkat 
Published: November 2022

As Lithium-Ion Batteries (LIBs) becomes an essential part of the everyday life, fireproof electrolytes have become an important component of the next generation battery design without compromising the performance of the battery. Composite electrolytes (CEs), consist of polymer electrolytes with highly conducting ceramic particles are promising candidates to substitute currently commercialized LIBs with liquid electrolytes. So far, experiments with CEs have discovered positive and negative effect on the overall conductivity of the CEs in the presence of ceramic particles.1–4 Therefore, exists the conflict weather the CEs are the solution to overcome the disadvantages of all-liquid and all-solid electrolytes.
In this work, a 2-Dimensional CE with a uniform ceramic particle size distribution is studied via continuum modeling. we analyze the effect of interface between polymer and ceramic particle on the overall conductivity and transference number of the CEs to guide experimentalist to fabricate these interfaces carefully. It is concluded that the interplay between ohmic resistance and polymer conductivity at the polymer and ceramic particle interfaces can explain the conflicts observed in the literature. The Ohmic resistance at the interface is a critical parameter that determines whether ceramic particles enhance the overall conductivity or not. Finally, CEs does meet the criteria of the conductivity and transference number requirement in order to use in the EVs.5

References:
(1) Cheng, S. H.-S.; He, K.-Q.; Liu, Y.; Zha, J.-W.; Kamruzzaman, M.; Ma, R. L.-W.; Dang, Z.-M.; Li, R. K. Y.; Chung, C. Y. Electrochemical Performance of All-Solid-State Lithium Batteries Using Inorganic Lithium Garnets Particulate Reinforced PEO/LiClO4 Electrolyte. Electrochimica Acta
2017, 253, 430–438.
(2) Zagórski, J.; López del Amo, J. M.; Cordill, M. J.; Aguesse, F.; Buannic, L.; Llordés, A. Garnet–Polymer Composite Electrolytes: New Insights on Local Li-Ion Dynamics and Electrodeposition Stability with Li Metal Anodes. ACS Appl. Energy Mater.
2019, 2 (3), 1734–1746.
(3) Bonilla, M. R.; García Daza, F. A.; Ranque, P.; Aguesse, F.; Carrasco, J.; Akhmatskaya, E. Unveiling Interfacial Li-Ion Dynamics in Li 7 La 3 Zr 2 O 12 /PEO(LiTFSI) Composite Polymer-Ceramic Solid Electrolytes for All-Solid-State Lithium Batteries. ACS Appl. Mater. Interfaces
2021, 13 (26), 30653–30667.
(4) Choi, J.-H.; Lee, C.-H.; Yu, J.-H.; Doh, C.-H.; Lee, S.-M. Enhancement of Ionic Conductivity of Composite Membranes for All-Solid-State Lithium Rechargeable Batteries Incorporating Tetragonal Li7La3Zr2O12 into a Polyethylene Oxide Matrix. J. Power Sources
2015, 274, 458–463.
(5) Kim, H.-K.; Srinivasan, V. Status and Targets for Polymer-Based Solid-State Batteries for Electric Vehicle Applications. J. Electrochem. Soc.
2020, 167 (13), 130520.
Finite-Element Simulation for Ion Co-Intercalation Chemistry on Si Anode at Lithium-Ion Half-Cell
Authors: Yang Zicheng , Cora Saida , Briselli Vincent , Sa Niya 
Published: November 2022

The increasing demand for higher capacity energy storage technologies is rapidly becoming an important consideration in the development of EV and related energy storage devices. Silicon is one promising solution as an earth-abundant element with a higher capacity than the more commonly used graphite anode of a lithium-ion battery. However, silicon anodes face unique challenges with volume expansion, notable during lithium ion intercalation and the stability of the SEI layer. To solve this problem, some recent research efforts discovered introducing a co-intercalation ion in the traditional lithium electrolyte Gen2 increases the coulombic efficiency, capacity, and stability of the silicon anode, but its mechanism of action remains unclear.
In this work, in combination with experimental measurements we demonstrate the use of Newman's P2D Lithium Model in COMSOL together with the Butler-Volmer equation and concentrated solution theory to describe cation co-intercalation into the porous silicon anode material. Experimental data indicates that phase formation and transformation coincide with ion insertion, as reflected in the current response signal. Both the original ion intercalation and the foreign ion intercalation are reflected by CV generated by our model under the influence of model parameters, such as the variable speed of potential changed per second. As designed, our model can be extended towards general application in the cointercalation system and understanding of the foreign ion effect.
Insoluble Solid Organic Catalysts for Non-Aqueous Lithium-Air Batteries
Authors: Renault Stéven , Poizot Philippe , Castro Laurent 
Published: November 2022

The chemistries based on the Li-O2 couple in aprotic electrolyte seem promising to provide ultrahigh-energy density values and outperform the current LIB technology. The main targeted application is to power electrified vehicles, with the hope of achieving high driving range. Unfortunately, serious side-reaction issues have plagued their development for practical applications so far. For example, during the discharge process, undesired insulating products are formed instead of lithium peroxide. Moreover, the blocking/clogging effect on the air electrode due to a deposition process leads to an overpotential during both the discharge (Oxygen Reduction Reaction: ORR) and charge processes (Oxygen Evolution Reaction: OER), which results in electrode degradation, electrolyte decomposition and precocious cell failure.
A promising strategy to reduce these overpotentials is the use of organic redox mediators by taking advantage of their tunability. For several years, our group has been developing lithiated organic materials with average redox potentials close to the O2/Li2O2 redox couple (2.96 V vs Li+/Li0). We here report the effect of Li2DAnT (alone or in combination with Li4-p-DHT [1]) and Li4-DHNDC [2] on the cycling behavior of Li-O2 batteries and their influence on ORR and OER processes.

References

1) S. Renault, et al., PCT Patent WO 2021/148835 A1.
2) S. Renault, et al., PCT Patent WO 2021/148836 A1.

Figure 1
Iron Fluoride Confined in Carbon Nanofibers for Lithium and Sodium Battery Cathodes
Authors: Fu Wenbin , Sun Zifei , Magasinski Alexandre , Yushin Gleb 
Published: November 2022

Today, lithium (sodium) battery cathodes based on the intercalation/deintercalation of lithium (sodium) ions are approaching their instinctive limits, which remains a big challenge for the development of next-generation batteries. Iron fluorides (FeF2, FeF3), a potential alternative to current intercalation cathodes, are believed to offer much higher capacity and higher energy due to their reversible conversion reactions during charging/discharging. However, their structural degradation and capacity fading upon cycling could block the road to future applications.
To address these issues, we developed a stable iron fluoride cathode based on nanoconfined FeF3 in carbon nanofibers for lithium and sodium batteries. The produced FeF3
/C nanocomposite is free-standing and can be produced using an electrospinning-based strategy with post carbonization and fluorination process. When tested in lithium cells, the nanocomposite can exhibit a high specific capacity up to 550 mAh g–
1 and a cycle stability over 400 cycles [1]. When tested in sodium cells, the nanocomposite can deliver a high specific capacity of 230 mAh g–
1 in sodium-difluoro(oxalato)borate (NaDFOB) electrolyte [2]. The performance especially cycle stability was further improved by atomic layer deposition (ALD) of Al2O3 coating on nanofiber surface [3]. We find the coating can reduce the direct contact between active material and liquid electrolyte, minimize active material dissolution and significantly improve the overall performance.
[1] W. Fu, E. Zhao, Z. Sun, X. Ren, A. Magasinski, G. Yushin, Iron Fluoride–Carbon Nanocomposite Nanofibers as Free-Standing Cathodes for High-Energy Lithium Batteries, Advanced Functional Materials 28 (2018) 1801711.
[2] Z. Sun, W. Fu, M.Z. Liu, P. Lu, E. Zhao, A. Magasinski, M. Liu, S. Luo, J. McDaniel, G. Yushin, A nanoconfined iron(iii) fluoride cathode in a NaDFOB electrolyte: towards high-performance sodium-ion batteries, Journal of Materials Chemistry A 8 (2020) 4091-4098.
[3] Z. Sun, M. Boebinger, M. Liu, P. Lu, W. Fu, B. Wang, A. Magasinski, Y. Zhang, Y. Huang, A.Y. Song, M.T. McDowell, G. Yushin, The roles of atomic layer deposition (ALD) coatings on the stability of FeF3 Na-ion cathodes, Journal of Power Sources 507 (2021) 230281.
A New Class of 2D Materials - Quaternary Derived Nanostructures - and Their Polysulfide Anchoring Capabilities in Lithium Sulfur Batteries
Authors: Cardoza Neal A. , Pereira Rhyz , Badr Hussein , Pai Rahul , Natu Varun , Carey Michael , Barsoum Michel W. , Kalra Vibha 
Published: November 2022

Metal-sulfur battery chemistries have garnered a lot of interest due to their 5-10 fold higher theoretical energy densities compared to state-of-the-art lithium-ion batteries, in addition to the abundance and environmental benignity of sulfur. However, the insulating nature of sulfur, the formation and shuttling of polysulfides, are still major drawbacks. In this work we started with quaternary ammonium salts or quat derived nanostructures (QDNs), synthesized using a facile bottom-up reaction, directly from commercial 3D bulk solids1. This approach leads to better functionalization, facile tunability, and higher active sites. Moreover, these materials self-assemble into a plethora of microstructures – from individual anatase-based 1D nanoribbons 6x102 Å in cross-section to 2D flakes to mesoscopic particles, both comprised of 1D nanoribbons - depending on the synthesis and washing parameters. Here we use QDNs made from commercial titanium carbide (TiC) reacted at 50℃ for 5 days, washed with 5M lithium chloride, and freeze dried after filtration. These TiC QDNs are simply hand ground with sulfur in a 50:50 ratio by weight, to create a sulfur TiC QDN composite. This composite was then used to make a slurry with carbon black and binder, in a ratio of 70:20:10 respectively. We obtain specific capacities of 800 mAh.g-1 at 0.5 C after 300 cycles seen in Figure 1. The anatase-based 1D nanoribbons, that assemble into 2D layers, traps the polysulfides by forming thiosulfate species and Lewis acid-base interactions with the titanium, confirmed by post-mortem X-ray photoelectron spectroscopy. Additionally, these interactions were confirmed visually with the 2D QDNs adsorbing polysulfides, after 7 days the 0.5mM solution of polysulfides appeared clear in comparison to the still yellow hue of the polysulfides seen with carbon black seen in Figure 2. These interactions are further enhanced with the added functionalization of the 2D materials using non-polar di(hydrogenated tallow)benzyl methyl ammonium chloride (DHT) surfactant molecules.
1. H. O. Badr et al., Materials Today, S1369702121003813 (2022).

Figure 1
Carbon-Free High-Performance Cathode for Solid-State Li–O2 Battery
Authors: MA Sang Bok , Kim Mokwon , Lee Hyunpyo , Kwon Hyuk Jae , Yoon Gabin , Park Jung O. , Seo Dong-Hwa , Im Dongmin 
Published: November 2022

The development of a cathode for solid-state lithium-oxygen batteries has been hindered in practice by a low capacity and limited cycle life despite their potential for high energy density. Here, a previously unexplored strategy is proposed wherein the cathode delivers a specific capacity of 200 milliampere hour per gram over 665 discharge/charge cycles, while existing cathodes achieve only ~50 milliampere hour per gram and ~100 cycles. A highly conductive mixed ionic-electronic conductors (MIECs) are designed as a carbon-free cathode by first-principles calculations with a density functional theory (DFT) and nudged elastic band (NEB) to avoid the degradation associated with carbonaceous materials, implying an improvement in stability during the electrochemical cycling [1]. In addition, water vapor is added into the main oxygen gas as an additive to change the discharge product from growth-restricted lithium peroxide to easily grown lithium hydroxide, resulting in a significant increase in capacity [2]. Thus, the proposed strategy is effective for developing reversible solid-state lithium-oxygen batteries with high energy density. We will discuss on the systematic materials design and their electrochemical properties for solid-state lithium-oxygen batteries at the meeting.
References
[1] Sang Bok Ma et al., Advanced Energy Materials, 10 (2020) 2001767.
[2] Mokwon Kimet al., Science Advances, in press.

Figure 1