bluuebunny/crossref_metadata_2025 huggingface dataset:
Li-S Solid State Pouch Cell with Flexible SSE
Authors: Zhang Xiaoxiao , Qu Huainan , Qiu Dantong , Ding Tianyao , Liu Miao , Zheng Dong , Qu Deyang
Published: September 2023

An all-solid-state Li battery (ASSLB) is believed to be one of the most promising candidates to achieve high energy density of 500 Wh kg–1.After extensive exploration, several sulfide solid electrolytes have been synthesized with ionic conductivities in the order of 10–3 S cm–1 or even higher[1, 2]. With the successful development of various SSE materials, the major obstacle remaining is to demonstrate high energy density at a cell or battery level. Pelleting, dry processing, slurry coating, extrusion, and embedding into template have been explored for the manufacture of an SSE[3]. Despite the high energy density at the material-level and the electrode-level, the cell-level energy density of pellet format was still rather unsatisfactory (<50 Wh kg-1), which was mainly due to the thick SSE pellet (0.5–1 mm). Besides, the pelletizing process itself can only be limited to lab-scale research due to its high cost and poor practicability.

To boost cell-level energy density and render the mass production feasible, sheet-type cells with a thin SSE and a thick cathode have been recognized as a “must-develop” technology within the battery community. Dry processing of SSE and electrode was developed using sulfur carbon as the cathode and sulfide Li6PS5Cl as the electrolyte. A small amount of PTFE (0.75% in SSE and 1% in cathode) was applied as the binder. After grinding and rolling at 80 oC, the sheet-type cathode (2*3.5 cm2) and SSE (2.4*3.9 cm2) with respective thickness of 90 and 200 um were obtained. With LiIn alloy as the anode, the pouch cell delivered a discharge capacity of 1200 mAh g–1 at 0.05C after the first cycle activation at 60 oC. The results indicated the feasibility of dry processing technology to fabricate sheet-type SSE and electrode.

Figure 1. Voltage curves of the pouch cell during the first three cycles tested at 0.05C at 60 oC.

(1) Kato, Y.; Hori, S.; Saito, T.; Suzuki, K.; Hirayama, M.; Mitsui, A.; Yonemura, M.; Iba, H.; Kanno, R. High-Power All-Solid-State Batteries Using Sulfide Superionic Conductors. Nat. Energy
2016, 1, 1–7.

(2) Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K.; Mitsui, A. A Lithium Superionic Conductor. Nat. Mater.
2011, 10, 682–686.

(3) Emley, B.; Liang, Y.; Chen, R.; Wu, C.; Pan, M.; Fan, Z.; Yao, Y. On the Quality of Tape-Cast Thin Films of Sulfide Electrolytes for Solid-State Batteries. Mater. Today Phys.
2021, 18. 100397.

Figure 1
Composite Solid Electrolyte Composed of 3D Ceramic Ion Transport Channel and in-Situ Formed Polymer Matrix
Authors: Kim Jong Min , Nguyen An-Giang , Park Chan-Jin
Published: September 2023

Rechargeable lithium-ion batteries (LIBs) with high energy density and excellent cycling performance have been widely used as portable power supplies for consumer electronics. In recent years, LIBs have expanded their applications to electric vehicles (EVs) and large energy storage systems (ESSs). Existing LIBs use liquid electrolytes, which have safety issues such as inflammability, leakage, and explosion. All-solid-state lithium-ion batteries (ASSLIBs) using various solid electrolytes, such as inorganic electrolytes and polymer electrolytes, have been extensively studied to alleviate safety issues and improve energy density. In addition, composite solid electrolytes (CSEs), which combine the advantages of ceramic and polymer electrolytes, are of particular interest. However, CSE based on a polymer matrix has low ionic conductivity at room temperature, making it difficult to use as an electrolyte for high-performance ASSLIB. In this study, we designed a highly efficient 3D LAGP framework for lithium ion transport that enhances the overall conductivity of CSE. This stiffer 3D LAGP structure also inhibits the growth of Li dendrites. The polymer component of CSE is manufactured using thermal polymerization of vinyl ethylene carbonate (VEC). In addition, excellent electrode-electrolyte interface properties were achieved using in-situ thermal polymerization technology. The optimized CSE exhibited high ionic conductivity of 0.79 mS cm-1 and excellent potential stability up to 5.09 V vs. Li/Li+ at 30 °C. The Li/CSE/NCM811 cells showed excellent rate performance and cycling potential. Therefore, a CSE composed of a 3D LAGP framework and a VEC-based polymer can be used as a potential electrolyte for ASSLIBs.
Li7La3Zr0.5Nb0.5Ta0.5Hf0.5O12 High-Entropy Li-Garnet with Fine Microstructure and Promising Properties
Authors: Fu Zhezhen
Published: September 2023

We demonstrated the processing of Li7La3Zr0.5Nb0.5Ta0.5Hf0.5O12 high-entropy Li-garnet with promising properties for lithium batteries. We first synthesized the LLZNTH Li-garnet powders which have a single cubic garnet phase without any secondary phases as well as uniform elements distributions. We further studied the formation, sintering, and mechanical properties of Li7La3Zr0.5Nb0.5Ta0.5Hf0.5O12 (LLZNTH) high-entropy Li-garnet with the comparison with Li6.75La3Zr1.75Ta0.25O12 (LLZT). The study indicates that the LLZNTH sample has a finer particle size after both calcination and ball mill than LLZT. Both samples can be densified to a relative density up to ~93-94% at a temperature of 1100°C, however, they show significant different sintering and grain growth behaviors. The LLZNTH sample takes 16 hours to reach the maximum relative density while the LLZT sample only needs 12 hours. LLZNTH sample has a significant lower grain growth parameter due to sluggish effects of high-entropy compounds so that it maintains fine microstructures (grain size ~10µm) than the LLZT sample (grain size over 100 µm). Due to the fine microstructures, the LLZNTH sample shows both higher flexural strength (84.8±6.9MPa compared with 47.9±10.1MPa) and hardness (8.5±0.8GPa compared with 7.7±0.4GPa) than the LLZT sample. Ionic conductivity characterizations indicate that the LLZNTH sample shows a moderate conductivity of 4.67×10-4 S cm-1 at room temperature and a low activation energy of 0.25eV.

Figure 1
In-Situ Thermo-Mechanical Characterization and Strain Engineering of Lipon Thin Films
Authors: Cai Truong , Westover Andrew , Kalnaus Sergiy , Dudney Nancy , Sheldon Brian W.
Published: September 2023

High temperature multi-optical-stress sensor (HTMOSS) has been used to characterize the coefficient of thermal expansion (CTE) and yield stress of 1-micron thick LiPON films. Six fully dense, amorphous films were deposited on glass and sapphire substrates. The films were then annealed at temperatures ranging from 80 to 200 C for 3 hours. The CTE of LiPON is found to be approximately 4.1e-6, and argued to be independent of the substrate type. Because of this intermediate CTE value, by varying the substrate, we could impose either tension and compression due to thermal mismatch to the film. We observed further that the yield stress of the film is approximately 60 MPa under compression and 100 MPa under tension. Using constant-load hold at and beyond yield point, the films were found to relieve the stress developed during heating with visco-plastic deformation, which led to permanent residual stress during cooling as high as 120 MPa in either tension or compression depending on substrate type. We also found that at annealing temperature higher than 140 C LiPON lost ductility which could be due to composition changes as indicated by XPS measurement. The stress-relief mechanism at constant-load indicates that LiPON may be beneficial as a protective layer against dendrites penetration. Moreover our experimental platform proves that it's an effective method to engineer strain into thin-film solid electrolytes that could be extended to other materials like LLZO or sulfide electrolyte.
Organic Cathode for Lithium Batteries, Enabled by Solid-State LLZO Separator
Authors: Tucker Mike C , Jonson Robert A , Battaglia Vincent
Published: September 2023

Small organic molecule quinones are promising as cathode active materials for Li batteries. They have high theoretical capacity (up to ~500 mAh/g) at moderate voltage (2 to 3V vs. Li/Li+). However, in conventional Li-ion batteries with liquid electrolyte, they dissolve and cross through the membrane, leading to reaction with the Li anode. To solve this issue, we employ a dense lithium garnet solid electrolyte (LLZO) as the separator to block transport of the organic cathode material. This work demonstrates solid electrolyte/liquid catholyte hybrid battery cells with metallic Li alloy as the anode and lawsone, a biologically-derived quinone, as the cathode. LLZO is used as a separator and effectively prevents dissolved cathode material from meeting the anode. Lawsone LLZO hybrid cells reached cathode utilization of up to 67% based on lithiation of both carbonyl groups, and had little self-discharge compared to liquid cells. A side-reaction at low voltage is identified as the main source of capacity fade. Nevertheless, use of a solid electrolyte is shown to be a promising approach to enable use of soluble organic cathode active materials.
Design of Solid Electrolytes to Enable Direct Cathode Recycling in All-Solid-State Lithium Metal Batteries
Authors: Helms Brett
Published: September 2023

All-solid-state lithium metal batteries are thought to be safer when used in electric vehicles with large powertrains. During the manufacturing of cathodes and separators from solid electrolytes, interphases generated between particulates at high pressure and temperature make deconstructing solid-state batteries exceedingly difficult. Here, I will describe a new approach for creating all-solid state batteries that are readily deconstructed and whereby all components of the battery can be dissociated from the other, enabling direct cathode recycling. Key to our design is the solid electrolyte, which assembled from ion-transporting components that may also be disassembled using a simple solvent-assisted process. Batteries featuring this solid electrolyte operate for hundreds of cycles at EV-relevant C-rates with both LFP and NMC cathodes, showing 80% capacity retention over that timeframe. More importantly, second-life batteries after direct cathode recycling indicate we can recovery 90% of the original capacity from the cathodes and sustain it for hundreds of additional cycles at those rates.
Effect of Surface Nature on Stripping of in Situ li Anodes and Enhancement of Its Stripping Capacity
Authors: Lee Kiwoong , Sakamoto Jeff
Published: September 2023

Li-metal solid-state batteries (LMSSBs) have been considered disruptive technologies for the widespread adoption of EVs due to their improved safety and higher energy density. Recently, in situ Li anode formation on solid-electrolytes (SEs) has garnered interest owing to its low manufacturing cost, high purity, and enhanced energy density. Thus, there have been intense efforts to understand the mechano-electrochemical properties of in situ Li anodes. Our previous work has demonstrated that the accessible capacity of in situ thin Li decreases as current density increases. This result indicates that more Li will remain inaccessible as the stripping rate increases, leading to the reduced energy density of LMSSB cells. To minimize the amount of inaccessible Li at high stripping rates, it is essential to investigate the factors affecting the stripping capacities of in situ Li and devise a new way to achieve enhanced stripping capacities at high stripping rates.

First, this study focuses to understand the correlation between the stripping capacity of in situ thin Li and the nature of the surface. This study demonstrates that the nature of the surface can dramatically affect the stripping capacity. When discharging at room temperature and 3 mA/cm2, approximately 50% of the accessible capacity of in situ plated Li was achieved.

Furthermore, this study demonstrates that stripping Li under conditions that more closely resemble an EV duty cycle improves the accessible capacities at high stripping rates. By introducing short intermittent rest periods during stripping, the Li/LLZO interface can be relaxed as Li vacancies at the interface can be moved away, preventing voids to forms. Also, even if voids form at the interface, the growth of voids can be delayed because of rewetting mechanisms during the rest periods.

This study is expected to not only provide insight into the stripping properties of in situ Li, but also suggest future guidelines for the practical discharge protocols of anode-free LMSSBs with commercially-relevant discharge rates.
(Invited) Ion Transport and Interface Resistance in Polymer-Based Composite Electrolytes and Composite Cathode
Authors: Chen Xi
Published: September 2023

Solid-state electrolytes are promising to enable the next generation batteries with higher energy density and improved safety. However, each major class of solid electrolytes has intrinsic weaknesses. By combining different classes of solid electrolytes, such as a polymer electrolyte and an oxide ceramic electrolyte, one can potentially overcome the intrinsic weaknesses of each component and develop a composite electrolyte to achieve high ionic conductivity, good mechanical properties, good chemical stability, and adhesion with the electrodes.

In this presentation, we show that the interfacial resistance strongly affects the ionic conductivity of polymer/oxide ceramic composite electrolytes, in both the ceramic-in-polymer design where ceramic particles are dispersed within the polymer electrolyte matrix as well as the polymer-in-ceramic design where a three dimensionally interconnected ceramic scaffold is developed. The quantification of the interfacial resistance, the origin of this resistance, as well as the strategies to minimize it are discussed.

In a second case, we examine the effect of interfaces on ion transport in a polymer based composite cathode consisting of LiFePO4 (LFP), carbon and poly(ethylene oxide) (PEO) with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The structure and dynamics of PEO and lithium ion mobility are studied by small angle neutron scattering and quasi-elastic neutron scattering. The results show that Li ion mobility in PEO/LiTFSI in the composite cathode is only 30% of the bulk electrolyte. This suggests a key bottleneck that limits the rate performance of polymer-based solid-state batteries originates from the sluggish ion transport in the polymer electrolyte confined in the cathode.
Plasma Modification of Interfaces in Ceramic Nanofiber–Polymer Electrolytes for Lithium Metal Batteries
Authors: Mu Xiaowei , Wang Anyang , Wu Nianqiang
Published: September 2023

Ceramic–polymer composite electrolytes hold a great promise as next-generation electrolytes because of strong mechanical properties and wide electrochemical stability window. However, it remains challenges in improving ionic conductivity and lithium ion transference numbers. In this work, plasma treatment has been performed on Li0.33La0.557Ti0.995Al0.005O3 (LLATO) nanofibers. The treated nanofibers are then incorporated with a polymer matrix to form a composite electrolyte. Plasma treatment has modulated oxygen vacancies, functional groups, polarity, and interfacial interaction of LLATO-polymer. This has improved lithium ion transport at interface of LLATO-polymer electrolyte. As a result, the LLATO-polymer electrolyte shows enhanced ionic conductivity and mechanical performance. This work has implication in design of ceramic-polymer composite electrolytes for solid state lithium metal batteries.
Succinonitrile-Lithium Salt Composite As a Solid Catholyte for Llzo-Based All-Solid-State Batteries
Authors: Go Wooseok , Tucker Mike C , Doeff Marca M.
Published: September 2023

All-solid-state batteries (ASSB) have come into the spotlight as next-generation batteries because of their potential high energy density and low flammability. LLZO (Li7La3Zr2O12) is a prominent solid electrolyte material for ASSBs due to its high ionic conductivity (>1 x 10-4 S/cm at room temperature) and compatibility with Li metal. However, for its use in ASSBs, there are challenges including forming intimate contact with the active electrode material. Because both LLZO and the cathode active material are rigid, employing a soft solid catholyte between them can be a solution to ensure intimate contact. The solid catholyte must be ionically conductive, and stable against oxidation (> 4.5 V vs. Li/Li+).

Organic Ionic Plastic Crystals (OIPC) are a class of materials that is soft and waxy at room temperature. When the OIPC is mixed with Li salts, the mixture has high ionic conductivity and a wide electrochemical window. Succinonitrile (SN) is an OIPC material, and SN with Li salts are reported to have high ionic conductivities (> 1x10-4 S/cm), good oxidation stability (>5 V vs. Li/Li+), and low flammability as well [1][2]. Despite the favorable properties of the SN-Li salt composite, poor chemical stability with Li metal makes it difficult to use it alone as a solid electrolyte [1]. For its use as a solid catholyte, chemical stability with Li metal is not an issue, making it a prominent candidate material. However, studies for its use as a solid catholyte with LLZO are limited.

In this talk, we describe the properties of Succinonitrile-Lithium salt composites focusing on their suitability as solid catholytes in LLZO-based ASSBs. SN is mixed with different kinds of Li salts including LiTFSI and LiBOB to form composites. Their electrochemical properties are compared and the contact between the composite and LLZO is observed. The performance of all-solid-state cells with the mixtures will also be evaluated at room temperature. It is hoped that this work can motivate efforts toward developing LLZO cells using OIPC materials.

[1] Alarco P.J, et al Nat. Mater., 3, 476 (2004)

[2] Effat M.B, et al J. Power Sources, 226802, 436 (2019)
Restoring the Crystal Structure of Single-Crystalline High Ni Ncm with Synthetic Heat Treatment Profile Control
Authors: Kim Juseong , Hong Kijoo , Jung Yongjo , Lee Jiho , Kim Yong Il , Lee Sunhwa , Nam Sang Cheol
Published: September 2023

Single-crystalline high Ni NCM is regarded as a next generation cathode candidate for high-energy lithium ion batteries with great potential due to its advanced crystal structural and chemical stability. The synthesis of single-crystalline high Ni NCM was studied using in-operando heating XRD.

The change of the crystal structure of single-crystalline NCM was observed while raising the synthesis temperature. The synthesis was carried out in two steps, with the first step at 860 degrees to form the phase and grow the particle size, and the second step around 740 degrees to recover the collapsed structure by the first heat treatment. XRD data and Rietveld refinement results showed that the half width of (104) peak decreased over time in each step, but tended to increase as it moved from 1st step to 2nd step. In addition, it was confirmed that Li/Ni cation mixing maintained a high value at the 1st step but then steadily decreased at the 2nd step, which means relatively low temperature heat treatment is effective to recover crystal structural anti-site defects. To evaluate the electrochemical properties of structural restoration, coin half cell characteristics were evaluated. It was showed that the longer time of 2nd step of the heat treatment, the higher efficiency and capacity due to structural recovery.

Overall, this study provides insights into the synthesis of single-crystalline high Ni NCM and their crystal structure changes under real-time heating. This findings highlight the importance of the two-step synthesis process and the role of relatively low temperature of 2nd step heat treatment that can reduce Li/Ni cation mixing through structural recovery.
Freestanding Carbon Lattice-Based Composites for Lithium-Ion Batteries and Beyond
Authors: Romero Cameron , Gordon Kenneth , Fei Ling
Published: September 2023

Advancements in technology in conjunction with rising concerns of global warming have led researchers to search for sustainable and environmentally friendly energy sources. Wind and solar are promising alternatives to fossil fuels; however, storage of these renewable energy sources poses a significant threat to their viability. Lithium-ion batteries (LIBs) are ideal candidates to offset their intermittent nature, functioning as an excellent storage medium. In addition, LIBs have been playing a key role in personal electronics (computers, cellphones, etc.) and are ubiquitous. LIBs in electric vehicles (EVs) are also rising exponentially. However, lithium-ion batteries still face many challenges. Their electrodes are currently made based on the conventional wet film coating fabrication process that utilizes a slurry containing active material coated onto current collectors. This slurry coating technology challenges the production of thicker electrodes with less inactive components. Directly increasing electrode mass loading using the traditional slurry coating fabrication process introduces unavoidable issues such as slowed kinetics and binder degradation. Freestanding electrodes are a great alternative as they eliminate the need for inactive components (i.e., binder, additive carbon, and current collector) and shorten the fabrication process. In addition, it preserves the microstructures of the electrodes and alleviates agglomeration. In this work, carbon microlattice templates are designed and fabricated through the use of 3D stereolithography, which allows for design flexibility of any shape or geometry, followed by pyrolysis to create hard carbon. These hard-carbon templates are then subjected to grow iron sulfide that serves as active material, which has a theoretical specific capacity higher than that of commercial graphite. The design utilizes controlled microchannels that facilitate ion transport through charging and discharging cycles and carbon networks for fast electron transfer. The composites show much improved electrochemical performance. These results demonstrate the potential for advancing the development of composite electrodes and shed light on the enormous potential for developing high-energy density batteries using 3D printing.
Investigating Mechanisms Leading to Enhanced Performance of Carbon-Coated Si Anodes By Chemical Vapor Deposition Method
Authors: Arano Khryslyn G , Yang Guang , Aytug Tolga , Meyer Harry M , Armstrong Beth L. , Quinn Joseph , Browning Jim , Self Ethan , Wang Chongmin , Veith Gabriel M.
Published: September 2023

Prior research on carbon-coated silicon (Si@C) for Si-based lithium-ion batteries have shown improved electrochemical performance upon coating. However, the underlying mechanisms responsible for the enhancement in performance have not been fully explored and are typically attributed to the protective influence of the carbon coating around the Si particles as well as the improved electronic conductivity of the electrode. In this work, we investigate the contribution of coating on the processing of the electrodes as well as on the formed solid electrolyte interphase (SEI). Si@C particles were prepared by chemical vapor deposition (CVD) technique to achieve a homogeneous carbon layer on the Si surface. The influence of coating time as well as processing temperature was investigated. X-ray photoelectron spectroscopy (XPS), neutron reflectivity (NR) measurements, and transmission electron microscopy (TEM) reveal the coating characteristics such as its extremely thin nature, ~2.5 nm, allowing us to rule out the protective function of carbon coating to prevent Si volume expansion as the governing mechanism for the improved electrochemical behavior. Instead, Raman mapping of the electrodes reveal a uniform distribution of Si and carbon conductive additive, indicating that the coating on the Si particles can facilitate slurry processing which yields to more homogeneous electrodes. Consequently, this leads to the commonly reported improved electronic connections within the electrodes as supported by electrochemical impedance spectroscopy (EIS) data. Furthermore, SEI studies using XPS reveal similar SEI characteristics of the Si electrodes after cycling in half and full cell format. In summary, we assign the improved performance of Si@C on the beneficial effect of carbon coating on the processing of Si electrodes, but not on the electrochemical passivation.
Sodium Penetration in Nasicon Solid Electrolytes Under High Current
Authors: Hill Ryan Christopher , Spoerke Erik D. , Maraschky Adam M. , Peretti Amanda S. , Small Leo J. , Cheng Yang-Tse
Published: September 2023

High conductivity solid electrolytes, such as NaSICON, are poised to play an increasingly important role in safe, reliable battery-based energy storage, enabling a new class of sodium-based batteries. Coupled demands of high current densities (≥0.1 A cm-2) and low temperature (<200 °C) operation, combined with increased discharge times for long duration storage (>12 h), challenge the limitations of solid electrolytes. Here, we explore the penetration of sodium into NaSICON at 0.1 A cm-2 in a symmetric molten sodium cell. Previous studies of β’’-alumina proposed that Poiseuille pressure-driven cracking (Mode I) and low levels of electronic conductivity leading to ion-electron recombination (Mode II) can cause metal accumulation within solid electrolytes, but a comprehensive study at high current density is necessary. To understand and differentiate these modes in NaSICON, this work employs unidirectional galvanostatic testing of Na|NaSICON|Na symmetric cells at 0.1 A cm-2 over 23 1-hour intervals at 110 °C. While galvanostatic testing shows a relatively constant, yet increasingly noisy voltage profile, electrochemical impedance spectroscopy (EIS) between intervals reveals a significant decrease in cell impedance which can be correlated with sodium metal penetration, as observed in scanning electron microscopy (SEM). Significant sodium accumulation from the stripping-side electrode suggests that Mode II failure may be far more prevalent than previously considered. Further, these findings suggest that total charge transported per unit area (mAh cm-2), an important parameter for long duration storage, may be a more critical parameter than current density (mA cm-2) when examining solid electrolyte failure. Together, these results provide a better understanding of the limitations of NaSICON solid electrolytes under high current density and can guide the design of coatings to improve electrode-electrolyte interfaces.
Ion Transport in Polymer/Inorganic Composite Electrolytes – a Comparison between Broadband Dielectric Spectroscopy and Impedance Spectroscopy
Authors: Ock Jiyoung , Rahman Anisur , Gainaru Catalin , Sokolov Alexei , Chen Xi
Published: September 2023

Significant efforts have been made to develop composite electrolytes combining polymer matrix with Li-ion conducting inorganic solids for feasible construction of solid-state batteries. However, the Li-ion transfer kinetics at the interface between polymer/inorganic electrolyte is unfavorable for Li-ion conduction in the composite electrolyte because of the interfacial resistance and the activation energy barrier for interfacial Li-ion transfer. The activation energy barrier for the Li-ion transfer reaction at the interface is correlated with the interaction between Li-ion and polymer matrix in the polymer electrolyte, interaction between Li-ion and anions in inorganic electrolytes and the interaction between polymer and inorganic electrolytes, therefore, the electrolyte composition significantly affects the interfacial charge transfer kinetics in composites.

In this work, Li-ion transport properties in the composite electrolytes are investigated by using broadband dielectric spectroscopy (BDS) and impedance spectroscopy (IS). We particularly focus on Li-ion charge transfer at the polymer/inorganic interface from the dual ion conducting polymer to the single ion conducting polymer electrolytes with different Li-ion conducting salts such as LiN(SO2CF3)2 (LiTFSI) and (LiMTFSI) in vinyl ethylene carbonate (VEC) or polymerized vinyl ethylene carbonate (PVEC). The interfacial resistances of inorganic electrolytes Li0.34La0.56TiO3 (LLTO) in polymer electrolytes are elucidated. To further evaluate the polymer/inorganic electrolyte interfaces, various types of cell are assembled in a glove box filled with argon gas and characterized by a series of techniques such as BDS and IS. The Li-ion transfer kinetics at the interface significantly affects the Li-ion flux through the composite electrolytes and will be presented. In addition, we will present a systematic comparison between BDS and IS results in order to build connections between the two communities.

Acknowledgements

This work was supported as part of the Fast and Cooperative Ion Transport in Polymer-Based Materials (FaCT), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences at Oak Ridge National Laboratory under contract DE-AC05-00OR22725.
(Invited) Electrochemical Conversion Using 2D Transition Metal Dichalcogenides
Authors: Miller-Link Elisa , Wilder Logan , Aubry Taylor , Vigil-Fowler Derek , van de Lagemaat Jao , Ghoshal Debjit
Published: September 2023

We use 2D transition metal dichalcogenide (TMDC) catalysts to facilitate the nitrogen (N2) reduction to ammonia (NH3) or proton reduction to hydrogen (H2) via dark electrocatalysis. TMDCs are an important class of materials because they are 2D materials, where their quantum confined properties are easily manipulated for various applications. Transition metal-based catalysts offer a unique opportunity to exploit the d electrons and orbitals for N2 activation, where we specifically compare theoretically and experimentally MoS2, TiS2, and VS2. In addition, the 2D TMDC catalysts are highly tunable 2D catalysts, where the band energetics, surface functionalization, defects, and phase can be tuned to control the N2 and proton reactivity. We use indophenol and 1H NMR with isotope labeling to identify and quantify NH3 from the catalytic reaction; moreover, we use density functional theory to add insight into the 2D TMDC active site and reaction pathway. Through various attempts and iterations, we have many lessons learned about experimental and theoretical setup that will be communicated.
Heteroatom Incorporated Carbon Materials by Molten-State Synthesis
Authors: Tzadikov Jonathan , Shalom Menny
Published: September 2023

The insertion of heteroatoms with different electronegativity into a carbon network can significantly tune its electronic, optical, and electrochemical properties along with its chemical reactivity. The introduction of nitrogen and sulfur as electron donors or boron as an electron-withdrawing group into a carbon structure will alter its electronic states, (electro)catalytic properties, and chemical stability to oxidation and high temperatures. The traditional methods of synthesizing heteroatom-modified carbon matrices are carried out by solid-state reactions, chemical vapor deposition (CVD), and functionalization of the carbon materials. Although an impressively wide range of materials was synthesized by these methods, there are still some drawbacks that limit the progress in this field.

Herein we show a new, scalable, and easy way to synthesize heteroatom-incorporated carbon materials through a molten-state intermediate. The molten-state intermediate is achieved by using molten precursors, polycyclic aromatic hydrocarbons as carbon sources, and other molten precursors for the various heteroatoms, e.g., elemental sulfur or ammonia-borane complex (NH3BH3). Once heated above their melting point, these precursors form the molten-state intermediate, which induces strong covalent/coordination bonds between the heteroatoms and the sp2 carbon skeleton. This method enables the synthesis of BNCO, CS materials, and transition-metal-incorporated carbon/carbon-sulfur-oxide materials. The elemental composition is easily controlled within these materials (up to 30 wt.% boron, 20 wt.% sulfur, 30 wt.% nitrogen, while the transition metal ratio is kept within relevant materials), resulting in fine-tuning of the properties of the materials. These materials show promising performance towards electrochemical OER, Na-ion, and Li-ion batteries while illustrating the structure-activity relations.
(Invited) Computational Insights into Carbonaceous Materials for Energy Storage and Catalysis
Authors: Jiang De-en
Published: September 2023

In this talk, I will discuss our recent work in using computational tools to understand carbonaceous materials for energy storage and catalysis. First topic has to do with reversible low-temperature aqueous batteries where Cl2 liquid is plated inside nanoporous carbon; we will show how and where this reaction takes place by modeling carbons with various functional groups. Second, we will discuss sodium storage in triazine-based molecular organic electrodes; our computational effort focuses on the importance of hydroxyl substituents. Third, we will examine electrochemical CO2-to-ethylene conversion on metal-free covalent quinazoline networks-derived electrodes; the computation will be directed toward understanding the catalytic mechanism and the active sites on the functionalized carbon electrode.
(Invited) Multimodality Sensing and Actuation Using Nanocarbons
Authors: Cohen-Karni Tzahi
Published: September 2023

My team’s efforts are focused on the development and engineering of nanocarbons-based flexible platforms to interrogate and affect the properties of cells and tissue, with a specific goal to understand signal transduction (chemical or electrical) in tissue or complex 3D cellular assemblies. Our highly flexible bottom-up nanomaterials synthesis capabilities allow us to form unique hybrid-nanomaterials that can be used in various input/output bioelectrical interfaces, i.e., bioelectrical platforms for chemical and physical sensing and actuation. We have developed several approaches for monitoring (and affecting) the complex signal transduction in 3D cellular assemblies toward an organ-on-an-electronic-chip (organ-on-e-chip) platform for tissue maturation and disease progression investigations. Utilizing graphene, a two-dimensional (2D) atomically thin carbon allotrope, we can simultaneously record the intracellular electrical activity of multiple excitable cells with ultra-microelectrodes that can be as small as an axon (ca. 2µm). The outstanding electrochemical properties of the synthesized hybrid-nanomaterials allow us to develop highly efficient catalysts, that can be deployed as electrical sensors and (chemical) actuators. We demonstrated sensors capable of exploring brain chemistry and sensors/actuators that are deployed in a large volumetric muscle loss animal model. Finally, using the unique optical properties of nanocarbons in the form of graphene-based hybrid-nanomaterials and 2D nanocarbides (MXene), we have formed remote, non-genetic bioelectrical interfaces with excitable cells and modulated cellular and network activity with low needed energy and high precision. In summary, the exceptional synthetic control and flexible assembly of nanomaterials provide powerful tools for fundamental studies and applications in life science and potentially seamlessly merge nanomaterials-based platforms with cells, fusing nonliving and living systems together.
Advancement of the Electrochemical Performance of Stainless-Steel EEG Electrodes by Functionalizing with Carbon Nanotubes and Antibiofouling Molecules
Authors: Ruhunage Chethani , Hoque Md Abdul , Nawarathne Chaminda P , Alvarez Noe T
Published: September 2023

Understanding brain function and neurological disorders are essential to develop therapeutic strategies such as neuropharmacological medications and implantable biomedical tools to treat brain-related disorders. Implantable neural electrodes can deliver in-depth knowledge of brain activity and disorders by recording real-time brain signals. Epilepsy is an electrophysiological brain disorder caused by genetic factors or a brain injury. Electroencephalography (EEG) is a standard technique that provides more specific information about epilepsy. Both invasive and non-invasive EEG electrodes are used to study epilepsy and possess high temporal resolution. Invasive EEG electrodes are useful for localizing the brain's regions where epilepsy arises. EEG electrodes are mainly metal-based electrodes. Stainless steel, platinum, gold, tin, and silver are commonly used metals. Electrode material plays a critical role in the accuracy of the brain signal measurements and consistent performance in chronic applications. Stainless steel EEG electrodes are successfully used in EEG signal monitoring in vivo; however, stainless steel can undergo chloride-induced corrosion and biofouling over time. Corrosion and biofouling can negatively affect the impedance of the EEG electrodes resulting in poor signal recording and inconsistent performance. The current study reports the advancement of the performance of stainless-steel EEG electrodes by functionalizing with vertically aligned carbon nanotubes (CNTs) and zwitterionic phenyl phosphorylcholine (PPC) molecules. CNTs are conductive and biocompatible nanomaterial which have been successfully used for neural interfacing applications. The results show that the electrochemical performance of the EEG electrodes was significantly improved after functionalization with vertically aligned CNTs. Electrochemically grafting of zwitterionic PPC molecules onto CNTs further improved electrochemical performance and introduced anti-biofouling properties.
(Invited) Near-Infrared Photoluminescent Nanosensors for In Vivo Pharmacology and Inflammation Monitoring
Authors: Williams Ryan M. , Gaikwad Pooja Vinod , Ryan Amelia K. , Israel Atara R , Thahsin Myesha , Cohen Zachary , Rahman Nazifa
Published: September 2023

Rapid, minimally-invasive in situ detection of analytes in vivo remains a goal to study inflammatory signaling molecules and pharmacology of therapeutics. Towards this end, we are using the near-infrared photoluminescent properties of single-walled carbon nanotubes (SWCNT) to design sensors for use in live mice. The photostable, environmental-responsive, tissue-transparent emission of SWCNT is ideal for this application. Therefore, we are working toward in vivo analyte monitoring through a simple injection of hydrogel-encapsulated SWCNT sensors to localize signal to specific sites in the body. We are incorporating machine learning-based approaches coupled with molecular recognition to develop multiplexed SWCNT sensors for several inflammatory signaling proteins (cytokines) as well as chemotherapeutic agents. We are performing high-throughput near-infrared plate reader-based measurements to screen sensor responses prior to in vivo evaluation and testing with patient samples. We anticipate in vivo evaluation to lead to real-time understanding of inflammatory disease biology and drug pharmacology in the short-term, while long-term applications may include minimally-invasive and rapid clinical diagnostic development.
Design of Aptamer-Based Optical Nanosensors for the Detection of Interleukin-6
Authors: Ryan Amelia K. , Gaikwad Pooja Vinod , Cohen Zachary , Ahmed Yumna , Williams Ryan M.
Published: September 2023

Interleukin-6 (IL-6) is an inflammatory cytokine that has been recognized as a potential target for various autoimmune diseases, chronic inflammatory conditions, cancers, and more. Dysregulation of IL-6 is implicated in the genesis and progression of these disease states. For these reasons, detection of IL-6 and related biomolecules in vivo is of clinical interest to researchers of cancer and other inflammatory diseases. Single-walled carbon nanotubes (SWCNT) possess unique near-infrared fluorescent properties. When functionalized with a molecular recognition element, SWCNT can act as optical sensors that respond sensitively and specifically to a target analyte. Both antibodies and DNA aptamers can serve as molecular recognition probes, but aptamers may hold advantages for certain sensing applications due to their smaller size, higher stability, and lower production cost. We functionalized SWCNT with an analyte-specific DNA aptamer, which resulted in a nanosensor which responds selectively to IL-6. In vitro testing revealed significant shifts in the center wavelength and intensity of SWCNT fluorescence in response to IL-6. We then conducted several studies to investigate the mechanism of this sensor response in order to compare against traditional antibody-based sensors prior to ex vivo clinical sample testing. Rapid, minimally invasive detection of IL-6 as a chronic disease biomarker in vivo through DNA aptamer-functionalized SWCNT holds promise for early disease diagnosis, observation of disease progression, and evaluation of response to therapy.
Predicting Protein Corona Formation on Carbon Nanotubes
Authors: Landry Markita P
Published: September 2023

Engineered nanoparticles are poised to transform sensing, imaging, and delivery in biological systems. In particular, single-walled carbon nanotubes (SWCNTs) are uniquely suited for biological sensing and imaging due to their tissue-transparent and photostable near-infrared fluorescence. SWCNTs have been functionalized with various biomolecules, including synthetic peptides and proteins, to construct fluorescence-based nanosensors. Optimizing these -nanoparticle interactions is key in enhancing nanotechnology function. Yet, functionalized SWCNTs and other nanotechnologies more broadly suffer from as-of-yet unpredictable interactions with the biological environments in which they are applied: when nanoparticles are introduced into biological systems, endogenous proteins rapidly bind and often lead to decreased ability of the nanoparticles to perform their intended functions. As such, testing compatibility and function of nanotechnologies in biological systems requires a heuristic approach, where this unpredictable protein corona formation often prevents effective implementation.

In this work, we develop a classifier that identifies proteins binding to nanotubes based solely on the protein’s amino acid sequence. We build and validate our classifier using mass spectrometry-based quantitative proteomic data that characterizes proteins bound to SWCNT-based nanosensors. Distribution changes among protein properties allow us to determine protein features associated with increased likelihood of SWCNT binding, including high content of solvent-exposed glycines and non-secondary structure-associated amino acids. Understanding these key protein features that drive protein-nanotube binding informs the design of physics-based modeling approaches of such interfacial nano-bio interactions. Lastly, we apply the classifier to rapidly identify candidate proteins with high binding affinity to SWCNTs and experimentally validate adsorption of these proteins with a kinetic exchange assay to evaluate the predictive power of our model. In sum, this classifier provides a step toward undertaking the otherwise intractable problem of predicting protein-nanoparticle interactions.
Automated Open-Loop in Vitro photothermal TherapyUsing Near-Infrared Emitting Graphene Quantum Dots
Authors: Lee Bong Han , Stokes Gretel Ann , Valimukhametova Alina , Nguyen Steven , Gonzalez-Rodriguez Roberto , Coffer Jeffery , Naumov Anton V.
Published: September 2023

Graphene-based materials have been the subject of interest for photothermal therapy due to their high light to heat conversion efficiency. Graphene quantum dots (GQDs) are expected to both possess advantageous photothermal properties and facilitate visible and near-infrared (NIR) fluorescence image-tracking, while surpassing the other graphene-based materials in their biocompatibility. To test these capabilities several different GQD structures were synthesized using top-down (RGQDs from reduced graphene oxide) and bottom-up (HGQDs from molecular hyaluronic acid) approaches. RGQDs and HGQDs possess nanometer-scale sizes, are hydrophilic, and exhibit fluorescence throughout the visible and NIR. The high biocompatibility of RGQDs (1.5 mg/ml) and HGQDs (1.7 mg/ml) and substantial absorption tail in the NIR make them suitable for biological photothermal therapy applications. In aqueous suspensions of RGQDs and HGQDs, a low power (0.8 W/cm2) 808 nm NIR laser irradiation facilitates heating up to 46.0 and 47.0 °C, respectively, making them sufficient for cancer tumor ablation. In vitro photothermal studies were performed via cost-effective open-loop automated approach involving a 3D printer head controlling the laser and a thermocouple. These experiments are carried out in a 96 well plate to show that GQDs can facilitate HeLa cancer cells heating up to 54.5 and 43.5 °C from 37.0 °C, leading to the inhibition of cell viability down to 23%. GQDs’ fluorescence in the visible and NIR effectively tracks their intracellular accumulation verifying effects of photothermal treatment. The combination of therapeutic and imaging capabilities makes GQDs developed in this work highly prospective anticancer agents.
Modelling and Optimization of the Differential Surface Capacitance in Electrolyte-Gated Graphene Field-Effect Transistors
Authors: Deraspe Jean-Nicolas , Bazan Claudia M. , Béraud Anouk , Cote Sebastien , Bouilly Delphine
Published: September 2023

Graphene field-effect transistors (GFETs) are a promising avenue for the detection of biomarkers, allowing to envision improvements in diagnostic approaches for different types of cancer and other diseases. To enable such applications, the detection metrics of the devices must be optimized, including their sensitivity, selectivity, and stability. In particular, the capacitance of the device is one of the key determinants of the sensitivity of the electrical current of graphene to nearby changes in electrical potentials. In this presentation, we present our approach to optimize the surface capacitance of electrolyte-gated GFETs, by investigating theoretically and/or experimentally the effect of specific design parameters, including the graphene area, the removal of the backgate, and the passivation of electrodes. On the theoretical side, a mathematical representation of the device capacitance was established as an equivalent circuit of capacitors modelling for the quantum capacitance of graphene, the backgate capacitance, and the capacitance of electrical double layers in the electrolyte. On the experimental side, microchips of GFET arrays were assembled using microfabrication techniques on two types of substrates: a standard Si++/SiO2 wafer in which the doped silicon layer is used as a backgate, and a pure non-conducting borosilicate glass wafer in comparison. The capacitance of the devices was then measured using a custom parallel electrical prober by stepping the applied voltage in the solution and analyzing the resulting current response through a standard RC direct current model. We will present our analyses by comparing the relative impact of electrode passivation, backgate usage, and graphene area on the capacitance of devices. These results will enable a rational design of GFET devices with improved sensitivity for their use in applications such as biological, chemical, and gas sensing.