bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fabrication of Block Copolymer Templated Extended Surface Model Electrocatalysts By Atomic Layer Deposition and Physical Vapor Deposition
Authors: Bhattacharya Deepra , Arges Christopher G. 
Published: November 2022

Templating platinum group metal (PGM) nanostructures from microphase separated block copolymers (BCPs) allows for electrocatalytic activity to be studied on highly ordered, model surfaces with precisely controlled feature sizes and morphologies, thereby allowing catalyst electroactivity and stability to be probed as a function of nanoscale geometry. In our previous work [1], BCP templated electrocatalysts fabricated via incipient wetness impregnation of PGM precursors were tested for hydrogen oxidation/evolution and water-splitting activity on interdigitated electrodes using liquid and solid polymer electrolytes. This talk presents the fabrication of such electrocatalysts via Atomic Layer Deposition (ALD) and Physical Vapor Deposition (PVD) techniques (e-beam evaporation and sputtering). Self-assembled lamellae of poly-(styrene-block-methylmethacrylate) (PSbPMMA) thin films on Si wafer and glassy carbon substrates were subjected to 5 - 15 ALD cycles with trimethylaluminium (TMA) precursor to induce selective growth of alumina in the PMMA domains via Sequential Infiltration Synthesis. Thereafter, the polymer template was removed via Reactive Ion Etching (RIE) with oxygen plasma. The resultant alumina nanostructures templated from self-assembled PSbPMMA was then used as a substrate either for Platinum ALD with (trimethyl)methylcyclopentadienylplatinum(IV) precursor atop a Titanium Nitride adhesive layer, or for sputtering of Pt atop a Ti adhesive layer to obtain conformal Pt coatings of up to 20 nm in thickness. When e-beam evaporation was used, The PMMA domains were selectively removed by successive wet and dry etch steps, followed by deposition and lift-off. The PGM electrocatalyst nanostructures were characterized via a combination of electron microcopy, X-ray diffraction, and X-ray photoelectron spectroscopy, and the Pt content of the catalysts were determined via microwave leaching and digestion of the electrocatalyst thin film followed by Inductively Coupled Plasma Mass Spectroscopy. The nanostructured electrocatalysts were tested for oxygen reduction (ORR) activity in a conventional rotating disk electrode setup using 0.1 M perchloric acid electrolyte, and the ORR mass activities and active surface area were obtained.
[1] Bhattacharya, D., Arges, C. G., et al., Small,
2021, 17, 2100437
(Invited) ALD-Based Infiltration and Growth of Inorganic Materials in Polymers
Authors: Segal-Peretz Tamar 
Published: November 2022

Sequential infiltration synthesis (SIS) has emerged in the past decade as a powerful technique for growth of inorganic materials within polymers through atomic layer deposition (ALD) chemistry. In SIS, ALD precursors diffuse into the polymer and interact with it, leading to inorganic materials growth within the polymer’s free volume. If desired, the polymer can later be removed, yielding polymer-templated inorganic structures. Combining SIS with self-assembled block copolymer (BCP) patterns results in selective growth of inorganic materials within the polar domains of the BCP, making it an attractive method for directed templating of inorganic nanostructures. Thus, SIS opens a pathway for exploiting ALD precision and rich materials library in new 3D morphologies, defined by the polymer.
To build SIS design rules and expand SIS’ possibilities, we probed SIS growth and evolution at the atomic scale and explored the role of reversible polymer-precursor interactions in SIS growth through a plethora of methods: in-situ growth analysis (microgravimetry and FTIR), ex-situ high-resolution electron microscopy and extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT) calculations. This knowledge was then applied in fabrication by design of metal oxide fibers, porous particles, and membranes.
We fabricated Al2O3 and ZnO nanofibers, nanobelts, and core-shell fibers using designed growth profiles within electrospun polymer fibers. By controlling the organometallic precursors’ diffusion time, simultaneous but spatially controlled growth of Al2O3 and ZnO within the fibers was achieved, leading to the formation of metal oxide core-shell fibers. Self-assembled BCP particles were used to template porous metal oxide particles by selective growth of Al2O3 in the major block of the self-assembled structure. The uniform BCP assembly led to uniporous pores in the metal oxide particles. Finally, we utilized SIS and ALD within and onto BCP membranes for exceptional pore size control and pores’ surface engineering, yielding highly selective filtration membranes.
Interactive MD-DFT Model to Predict the Multi-Component Electrolyte Reduction within the Electrical Double Layer
Authors: Wu Qisheng , Qi Yue 
Published: November 2022

A typical liquid electrolyte for lithium (Li)-ion and Li-metal batteries is a liquid mixture with salt, solvent, and additives. The reduction products of the electrolytes form the solid-electrolyte interphase (SEI) layer, whose composition, heterogeneity and thickness largely determine the Li plating and stripping processes and thus the cycling performance. It is highly desirable to obtain atomistic insights into the reduction reactions of the electrolytes to help predict and control the formation of the SEI layer. The reduction reactions of the liquid electrolyte occur near the charged electrode surface within the electric double layer (EDL). The electrolyte structures within EDL must change under an electric field, which impacts the electrolyte reduction and SEI formation. This has been rarely considered in previous theoretical investigations of the reduction potentials and reduction products.
In this work, we have developed an interactive model combining molecular dynamics (MD) simulations and density functional theory (DFT) calculations to predict the multi-component electrolyte reduction within the EDL.[1] First, MD simulations, which can deal with thousands of atoms and even more, are used to capture the dynamics and statistics of the EDL structures. Then DFT calculations are used to compute the reduction products and corresponding reduction potentials of the representative clusters in the EDL. Finally, a formulation was proposed to calculate averaged reduction potential based on DFT-calculated reduction potentials of all the possible Li+-coordinated structures and their distribution probabilities obtained through MD analyses.
We have applied this new interactive MD-DFT model to two types of essential multi-component electrolytes, the carbonate-based electrolyte (LiPF6@EC:EMC) and the ether-based electrolyte (LITFSI@DOL:DME). We find in both electrolytes the Li+ ions within the EDL tend to have less coordination with other electrolyte species (salt anion, solvent and additive) compared to those in the bulk electrolyte. For LiPF6@EC:EMC, we reveal that FEC can enter into the EDL region and is favorable to be reduced, which helps form the F-containing SEI component (e.g., LiF). In addition, we have studied the effects of the FEC additive on LiTFSI@DOL:DME at various temperatures. We find that, at -40 °C, the number of F atoms that come near the electrode is largely increased after adding FEC, while no big change is observed at 20 °C. This explains that adding FEC is more effective in forming stable F-containing SEI and in promoting cycling performance at low temperatures.[2] Our simulations have also explained why ether based electrolyte works better than carbonate base electrolyte for Li metal anode.

Reference:

[1] Qisheng Wu,Yue Qi. Manuscript under preparation, 2022.

[2] Akila C. Thenuwara, et al. ACS Energy Lett. 2020, 5, 2411−2420
A Thermal Tanks-in-Series Model for Capacity Fade Validation Studies in Lithium-Ion Batteries
Authors: Thiagarajan Raghav Sai , Subramaniam Akshay , Kolluri Suryanarayana , Uppaluri Maitri , Preger Yuliya , Subramanian Venkat R. 
Published: November 2022

Lithium ion batteries are widely adopted due to their high energy density, low self-discharge rate and fast charging capabilities1. However, during their operation, capacity fade occurs as a result of various parasitic reactions causing loss of cyclable lithium ions. A dominant and widely studied fade mechanism is the formation of the Solid Electrolyte Interphase (SEI) layer caused by the reduction of electrolyte at the anode-electrolyte boundary. Temperature plays a crucial role on the electrochemical performance of individual cells, affecting the diffusivities of ions, kinetics of reactions and rate of degradation of the battery. Thermal battery models allow us to study the thermal behavior of cells and are often used for cell configuration optimization and thermal management system design2.
In literature, thermal models are incorporated with empirical and physics-based models to capture battery dynamics influenced by temperature. Empirical thermal models are simple and fast to solve but are applicable only for specific operating conditions and cannot capture electrochemical subtleties. Conversely, physics-based models use equations that incorporate transport phenomena and electrochemical reactions occurring in the cell. Common physics-based models are the Single Particle Model (SPM) and the Psuedo-2D (P2D) model. The P2D model is robust but computationally expensive3 and the SPM model does not capture electrolyte transport which has a non-linear temperature dependence.
The Thermal Tank-In-Series4,5 model is a systematically volume-averaged form of the P2D model with energy balance equations for the current collectors, cathode, separator and anode. This reduces the number of equations in the model and improves computational speed while maintaining accuracy. This model can be ideal to predict capacity fade during fast charging.
Extending on our previous work, we take the Thermal Tanks-in-Series model coupled with SEI layer formation for a single-cell sandwich and apply it to analyze capacity fade under different temperature cycling conditions. Experimental validation of the model will facilitate understanding of diffusive, kinetic and temperature effects on the growth of the SEI layer and cell capacity fade.

References

M. Pathak, S. Kolluri, and V. R. Subramanian, J. Electrochem. Soc., 164, A973–A986 (2017).

H. Liu, Z. Wei, W. He, and J. Zhao, Energy Convers. Manag., 150, 304–330 (2017).

V. Ramadesigan et al., J. Electrochem. Soc., 159, R31–R45 (2012).

A. Subramaniam, S. Kolluri, S. Santhanagopalan, and V. R. Subramanian, J. Electrochem. Soc., 167, 113506 (2020).

A. Subramaniam et al., J. Electrochem. Soc., 167, 013534 (2020).
Electrolytes for High Nickel Lithium-Ion Batteries
Authors: Liao Chen , Rodrigues Marco-Tulio F , Abraham Daniel P. , Gim Jihyeon , Son Seoung-Bum 
Published: November 2022

We have shown different strategies1, 2 in improving capacity retention and reducing impedance rise in modifying additives: in situ electrolyte additives to synthesize the beneficial lithium tetrafluorophosphate components3, 4 or dual-salt electrolytes1 for reducing cathodic impedance.
The cathodes we have tested have a LiNiO2 structure with an ultra-low amount of Co/Mn. An improved structural stability compared to that of LiNiO2 can be achieved while maintaining the high Ni content and high specific capacity. Using an optimal ratio of Ni/Mn/Co of 90/5/5 for a LiNi90Mn5Co5O2 cathodes,5 we here report the reduced reactivity of electrolytes using a combinatorial approach of reducing EC and introducing effective additives, targeting both a more robust SEI formation and a less resistive cathode electrolyte interface.
Multifaceted posttest analytical methods were used to understand the failure mechanism of the baseline cells and how additives/solvents approaches help the performance. For example, the new electrolytes prevent the transesterification reactions on anode surface, form a stable cathode interface, and mitigate structural damage on the cathode surface. Further analysis also investigated the how electrolytes protect the cathode bulk structure.
[1] J. Yang, M.-T. Fonseca Rodrigues, S.-B. Son, J. C. Garcia, K. Liu, J. Gim, H. Iddir, D. P. Abraham, Z. Zhang and C. Liao, ACS Applied Materials & Interfaces, 2021.
[2] J. Yang, I. Shkrob, K. Liu, J. Connell, N. L. Dietz Rago, Z. Zhang and C. Liao, Journal of The Electrochemical Society, 2020, 167, 070533.
[3] J. Yang, I. Shkrob, Q. Liu, N. L. Dietz Rago, Y. Liu, K. Liu, Z. Zhang and C. Liao, Journal of Power Sources, 2019, 438, 227039.
[4] I. A. Shkrob, B. Han, R. Sahore, A. P. Tornheim, L. Zhang, D. P. Abraham, F. Dogan, Z. Zhang and C. Liao, Chemistry of Materials, 2019, 31, 2459-2468.
[5] C. S. Yoon, M. H. Choi, B.-B. Lim, E.-J. Lee and Y.-K. Sun, Journal of The Electrochemical Society, 2015, 162, A2483-A2489.
Development of New Borate-Based Lithium Ionic Liquid for Next Generation Lithium-Ion Battery
Authors: Watanabe Hikari , Tabata Yuya , Han Jihae , Shitanda Isao , Umebayashi Yasuhiro , Itagaki Masayuki 
Published: November 2022

Solvate ionic liquids (SILs), which consist of a solvate ion and its counter ion, are expected as the electrolyte for the new generation Lithium-ion batteries [1]. Li-glymes SIL is an equimolar mixture of lithium salts and glyme of an oligoether such as triglyme and tetraglyme (Gn: CH3O-(CH2CH2O)
n
-CH3, n = 3 and 4). Li-glymes SIL shows favorable liquid properties like ordinary aprotic ionic liquids; negligible vapor pressure, practically non-inflammability, ionic conductivity and electrochemical stability, and so on. Watanabe et al. [2] have proposed that the specific Li+ ion hopping conduction occurs in the Li-glymes SIL. In Lithium-ion batteries with Li-glymes SIL, the desolvated Li+ ions are intercalated into graphite electrode, however, the co-intercalation of Li+ ion and glyme into the electrode occurs in the battery using the excess glyme electrolyte solution [3]. This suggests that the solvent activity affects the electrode reaction. In the present study, we prepared lithium ionic liquids with oligoether chains (Figure 1) and measured those physical and electrochemical properties.
Infrared spectroscopic (IR) measurements were carried out to identify the prepared lithium ionic liquids. An intense peak, which cannot be observed in the IR spectra of the raw materials, appears in approximately 1000 cm-1. This peak is attributable to B-O vibration mode, suggesting that the lithium ionic liquids are synthesized. We here define the new lithium ionic liquids as LiB(Gn)4 (n = 3 or 4). The ionic conductivities of LiB(G3)4 and Li(B4)4 are 0.20 and 0.37 mS cm-1, respectively. In addition, Li+ ion transport number is approximately 0.5 for both LiB(G3)4 and Li(B4)4., which is higher than that of electrolyte solution used in a commercial lithium-ion battery. This suggests that Li+ ion hopping conduction may occur via the exchange among glymes which are side chain of anion.

References

[1] C. Austen Angell, Y. Ansari, Z. Zhao, Faraday Discuss., 154, 9-27 (2012).
[2] K. Yoshida, M. Nakamura, Y. Kazue, N. Tachikawa, S. Tsuzuki, S. Seki, K. Dokko, M. Watanabe, J. Am. Chem. Soc., 133, 13121-13129 (2011).
[3] H. Moon, R. Tatara, T. Mandai, K. Ueno, K. Yoshida, N. Tachikawa, T. Yasuda, K. Dokko, M. Watanabe, J. Phys. Chem. C, 118, 20246-20256 (2014).

Figure 1
(Battery Division Technology Award) Understanding Metals' Roles in Layered Structure Oxides for High-Energy Lithium-ion Batteries
Authors: Lu Jun 
Published: November 2022

The ever-increasing requirements in the high-energy density of lithium-ion batteries (LIBs) and current bottlenecks in cobalt supply place restrictions on the development of the state-of-the-art cathode materials with fine-tuned chemical composition by substituting the cobalt with nickel and manganese. In the layered structure ternary systems (LiNi1-y-zMnyCozO2, NCM), three transition-metal ions play a distinctive role that determines the physicochemical properties. A comprehensive understanding of the basic contribution of each transition metal is critical for further complete replacing expensive cobalt.[1] Here, we demonstrate cobalt and manganese behaviors by comparing various layered oxides with different chemical compositions to reveal their corresponding contributions.[2] Our results affirmed that cobalt plays an undeniable role in fast degradation, and found that cobalt is more destructive than Ni at high voltages. Even the possible instability induced by manganese (III) Jahn-Teller distortion [3], Mn(IV) substitution in the lattice can effectively alleviate this destructive and enables a high potential functionality. By further regulating the chemical composition with a concentration gradient strategy, Co-enriched surface and Mn-enriched core design in Ni-rich particles determines a robust structure, which can effectively suppress the owing to the low stiffness of the surface and stable structure in the core region. With these fundamental discoveries, we provide a guide for developing the promising Co-free cathodes to meet the increasing demand for high-energy density LIBs.

References

[1] M. Li, J. Lu. Science, 2020, 367, 979-980.
[2] T. Liu, L. Yu, J. Liu, J. Lu, X. Bi, A. Dai, M. Li, M. Li, Z. Hu, L. Ma, D. Luo, J. Zheng, T. Wu, Y. Ren, J. Wen, F. Pan, K. Amine. Nat. Energy, 2021, 6, 277-286.
[3] T. Liu, A. Dai, J. Lu, Y. Yuan, Y. Xiao, L. Yu, M. Li, J. Gim, L. Ma, J. Liu, C. Zhan, L. Li, J. Zheng, Y. Ren, T. Wu, R. S.-Yassar, J. Wen, F. Pan, K. Amine. Nat. Commun., 2019, 10, 4721.
[4] T. Liu, L. Yu, J. Lu, T. Zhou, X. Huang, Z. Cai, A. Dai, J. Gim, Y. Ren, X. Xiao, M. V. Holt, Y. S. Chu, I. Arslan, J. Wen, K. Amine. Nat. Commun., 2021, 12, 6024.
From Order to Disorder: NMR Insights into Ionic Conduction in Li-Ion Solid Electrolytes
Authors: Sebti Elias , Jones Seamus , Segalman Rachel , Canepa Pieremanuele , Clement Raphaele J , Evans Hayden 
Published: November 2022

Nuclear magnetic resonance (NMR) spectroscopy provides detailed insights into the working principles of ionic and mixed conductors used in rechargeable battery applications. Notably, NMR is sensitive to crystalline, disordered or even amorphous phases that arise during electrochemical cycling, and can provide atomic-level structural information, as well as insights into the dynamics of ion motion. In this talk, I will present our recent work on Li-ion conducting rocksalt halides [1] and Li-conducting polymeric ionic liquids [2]. Using a combination of synchrotron X-ray diffraction/scattering, electrochemical impedance spectroscopy (EIS), solid-state NMR, pulsed field gradient NMR (PFG-NMR), NMR relaxometry, and first principles calculations, we provide a multiscale understanding of ion diffusion processes and link these findings to local structure features, crystallinity, and materials synthesis/processing conditions.

[1] Sebti, E., Evans, H., Chen, H., Richardson, P., White, K., Giovine, R., Koirala, K. P., Xu, Y., Gonzalez-Correa, E., Wang, C., Brown, C., Cheetham, A., Canepa, P., Clément, R.*, "Stacking Faults Assist Lithium-Ion Conduction in a Halide-Based Superionic Conductor", J. Am. Chem. Soc., accepted. DOI: 10.1021/jacs.1c11335.
[2] Jones, S., Nguyen, H., Richardson, P., Chen, Y.-Q., Wyckoff, K., Hawker, C., Clément, R., Fredrickson, G., Segalman, R., "Design of Polymeric Zwitterionic Solid Electrolytes with Superionic Lithium Transport", ACS Cent. Sci., 8(2), 169-175 (2021). DOI: 10.1021/acscentsci.1c01260.
Detection of Li Deposition on Si/Graphite Anodes from Commercial Li-Ion Cells - a Post-Mortem GD-OES Depth Profiling Study
Authors: Fluegel Marius , Richter Karsten , Wohlfahrt-Mehrens Margret , Waldmann Thomas 
Published: November 2022

A new semi-quantitative method based on Post-Mortem glow discharge optical emission spectroscopy (GD-OES) depth profiling was developed to detect Li deposition on Si/graphite anodes. By means of the detected amounts of Li, Si and O in the GD-OES depth profiles, a corridor is determined, in which the minimum amount of Li deposition is found. Three different commercially available 18650 cell types containing Si/graphite as anode active material were acquired to evaluate the newly developed method. Those three cell types were initially characterized in detail by means of SEM/EDX, GD-OES, ICP-OES, and Hg porosimetry regarding their cell chemistry and electrode properties. One cell type was a high-power cell due to its high anode porosity and low anode coating thickness. The other two cell types were high-energy cells, which have thick anode coatings and low porosities.
We aged the cells at 45 °C until their SOH was 80% and analysed the aging behaviour using SEM, DVA, GD-OES, and in coin half-cells. GD-OES depth profiling revealed that no Li plating occurs during cycling aging at 45 °C. Contrary to this, Li plating was detected on the anodes of all three cell types by the new GD-OES method after the high-power cell was aged at -20 °C and the high-energy cells were aged to 0 °C.
Cells, which were previously aged at 45 °C until 80% SOH have afterwards been cycled under the same conditions, which led to Li plating in the fresh cells. Cell types exhibiting predominantly loss of anode active material (LAAM) as aging mechanism during the first aging at 45 °C, still suffered from Li plating during the second aging. However, if the main aging mechanism during the initial aging was loss of cyclable Li inventory (LLI), the cells did show a significantly reduced tendency for Li plating, even though the same conditions caused Li plating in the fresh cells.
Analysis of the aged anodes using coin half-cells revealed that the loss of anode material was caused by the deactivation of Si anode material. SEM images of the anode cross-section indicate that the deactivation is most likely mainly induced by the formation of a thick film surrounding the Si particles.
In combination with complementary methods like SEM, ICP-OES, and coin half-cell analysis, the newly developed GD-OES method yields in profound understanding of the aging behaviour of state-of-the-art Li-ion cells contain Si/graphite anodes.

Figure 1