bluuebunny/crossref_metadata_2025 huggingface dataset:
3D-Printed High Surface Area Electrodes and Advanced Flow Reactors for Bio-Compatible Electrochemical Reactions
Authors: Gutierrez Laura , Pritchard Avery , Jayathilake Buddhinie Srimali , Jue Melinda L. , Pang Simon H.
Published: December 2024

With the urgent need for emissions-free economies, bio-catalytic electrochemical processes such as electro-bio-methanation enable coupling of renewable energy harvesting with chemical energy storage and/or chemical synthesis. Electro-bioreactors offer high product selectivity and efficiency, eliminating the need for energy intensive separations. However, the electrochemical reaction rates of bio-catalytic processes are fundamentally constrained due to poor fluid distribution and ion transport near the electrode surface. Mass transport limitations in bioreactors alter the reactive surface environments and cause bio-catalytic stability issues. To address these challenges and achieve high volumetric productivities under bio-compatible conditions, we introduced additively manufactured, high surface area 3D electrodes and engineered flow cells. We characterized the effects of electrode geometry and structural parameters on electrochemical performance in abiotic media to develop structure property relationships. Using the hydrogen evolution reaction as a model system, we identified several high surface area structures that improve the fluid distribution within the reactor. Triply periodic minimal surface structures, like gyroids, enable higher volumetric productivities compared to conventional planar electrodes. These findings can be used to understand the role of electrode structure on electrochemical performance and the scaling behavior or bio-reactor flow cells utilizing 3D electrodes.

This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344
Collaborative Electronic Structure Modifier for Iron Single-Atom Electrocatalyst in High-Energy, Long-Cycle Lithium-Sulfur Batteries
Authors: Park Cheol-Young , Lee Jinwoo
Published: December 2024

In high-energy and long-cycle lithium-sulfur (Li-S) pouch cells, the cathodes often face limitations in their capacities and stability when subjected to practical electrolyte/sulfur (E/S), electrolyte/capacity (E/C), and negative/positive (N/P) ratios. In this study, an advanced cathode incorporating highly active Fe single-atom catalysts (SACs) is presented, enabling the formation of multi-stacked Li-S pouch cells with a total capacity reaching approximately 320.2 Wh/kg at the 1 Ah level. These cells exhibit low E/S (3.0), E/C (2.8), and N/P (2.3) ratios, along with high sulfur loadings of 8.4 mg/cm². The enhanced activity of the Fe SACs is achieved by manipulating their local environments using electron-exchangeable binding (EEB) sites. Introducing EEB sites comprising two different types of sulfur species, namely thiophene-like-S (–S) and oxidized-S (–SO₂), adjacent to Fe SACs enhances the kinetics of the Li₂S redox reaction by providing additional binding sites and adjusting the Fe d-orbital levels via electron exchange with Fe. While –S donates electrons to the Fe SACs, –SO₂ withdraws electrons from them. Consequently, the Fe d-orbital energy level can be regulated by varying the –SO₂/–S ratios of the EEB site, thus controlling their electron-donating/withdrawing characteristics. This desirable electrocatalytic behavior is maximized through the close contact of the Fe SACs with the sulfur species, all of which are confined within porous carbon structures.
Electrochemical Properties of Various Degradations in Rechargeable Batteries for LIB Diagnosis
Authors: Jang Il-Chan , Seo Joon Kyo , Song Jinju , Ma Jiyoung , Woo Jung-Je
Published: December 2024

Li ion batteries (LiB) offer high energy density, sufficient cycle life with low cost in energy storage industry. However, LIBs are complex systems which are not yet revealed completely for their degradation mechanism. In general, the loss of Lithium and Li plating during cycling, depletion and decomposition of the electrolyte, structural collapse of active materials and resistance increase are the most representative reasons for the degradation of LIBs. Therefore, accurate and fast diagnosis is critical for safe and long term use of batteries. To diagnose LIBs, we have focused to make degradation cells which have referred as reasons during cycling such as Li loss, Li plating. We fabricate various degradation cells as specified value and figure out the characteristic electrochemical proterties.
Playing with Carbon-Carbon Bonds
Authors: Wen Jianguo
Published: December 2024

The carbon atom stands out among elements for its ability to many allotropes. Among these, diamond and graphite are well-known. Diamond is the hardest material in nature due to its 3D network of sp3 covalent carbon bonds (1.54 Å). Conversely, graphite features a flat honeycomb lattice arrangement of carbon atoms, with countless layers weakly bonded through van der Waals forces. Within the graphene layer, a constituent of graphite, the sp2 covalent carbon bonds (1.42 Å) are shorter than that of diamond. It is of importance to form new carbon allotropes as well as understand transformation mechanism from graphite to diamond.

First, I will report the synthesis of bulk hexagonal diamond achieved via high-pressure and high-temperature treatment of single crystal graphite. This hexagonal diamond exhibits superior hardness to cubic diamond and showcases a dia-phite structure, with bond lengths resembling both diamond and graphite. Second, we experimentally observed the direct transformation pathway from graphite to cubic and hexagonal diamonds through an intermediate metastable graphite phase (i.e. orthorhombic graphite). Third, I will report the ultrafast formation of a transient 2D diamond-like structure under femtosecond laser irradiation using twisted graphene.

Overall, the creation of the new carbon forms clues that under modulated high pressure and temperature conditions, the great diversity of carbon covalent bonds could be assembled into carbon allotropes.

References:

Zeng, Z., Yang, L., Zeng, Q., Lou, H., Sheng, H., Wen, J., ... & Mao, H. K. (2017). Synthesis of quenchable amorphous diamond. Nature communications, 8(1), 322.

Luo, D., Hui, D., Wen, B., Li, R., Yang, J., Shen, X., ... & Wen, J. (2020). Ultrafast formation of a transient two-dimensional diamondlike structure in twisted bilayer graphene. Physical Review B, 102(15), 155431.

* Work performed at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357.
Glowing Graphene Quantum Dots Enhancing Photoelectric Transportation in Photosynthesis Carbon Trapping of Pteridophyta Fern
Authors: Su Yen-Hsun , Wu Shein-Fu , Wang Shu-Mei , Chang Chia-Wei
Published: December 2024

Pteridophyta fern plays an important role in photosynthesis to trap carbon in earth. The application of graphene also enhanced the quality of lettuce, resulting in reduced heavy accumulation in both leaves and roots and increasing in the levels of soluble sugar, protein, and vitamin C content. graphene was augmented the total size, surface area, average diameter, and the number of roots in lettuce roots. In this study, we investigated the response of plant growth by implanted different concentration of glowing graphene quantum dots in pteridophyta fern. Quantum yield and efficiency of chlorophyll fluorescence and were used to demonstrate photosynthesis function. Furthermore, CO2 exchange rate is determined to qualify the increasing carbon sink in plants. We found efficiency of donation electron to PSI (Fv/Fo), maximum quantum yield of PSII (Fv/Fm), performance index on absorption basis (PIABS) energy fluxes absorbed (ABS/RC) and trapped (TRo/RC) per reaction center (RC), primary photochemistry (ψo), electron transport rate (ETo/RC) and non-photochemical quenching for energy dissipation (DIo/RC) of Pteridophyta fern are enhanced after graphene is implanted in vein. Carbon trapping of pteridophyta fern is determined by Fv/Fm, PIABS, ABS/RC, TRo/RC, ψo, ETo/RC, and DIo/RC.
Study of Partial Silica Coating and Heat Treatment of PCNF to Improve Durability of Low-Temperature Fuel Cells
Authors: Lee Seon Ho , Lee Song Mi , Jung Doo-Hwan
Published: December 2024

In fuel cells, platinum is typically applied to the supporting carbon to improve performance and reduce platinum usage. Typically, Pt/C is used as a cathode catalyst for ORR. However, for practical use, the durability of Pt/C needs to be improved. The carrier material for catalysts used in fuel cells is carbon. There is a basic requirement to improve the carbon carrier near the high surface area, so that deposition of small platinum particles, improved stability under the operating conditions of the fuel cell, and high conductivity are realized. CNFs have attracted increasing attention in the past few years due to their high strength and chemical inertness, properties suitable for use as composites, electrode materials, and catalyst carriers. To improve the durability of PCNF as a catalyst for fuel cells, high-temperature heat treatment or silica coating methods are used. We would also like to determine whether heat treatment, silica coating, or both have any effect on improving the durability of PCNF, or whether the methods cause side reactions. The heating method is as follows: The obtained high-heat-treated PCNF was further heat-treated at 1700°C for 1 hour in a high-purity nitrogen stream. The ECSA of Pt/PCNF dropped to 30.6% of the initial value after 2000 cycles of potential cycling. However, Pt/Ht-PCNF and Pt/HtSi-PCNF ECSA showed a decline of 36.9% and 60.0%, respectively. In contrast, this study demonstrates that even as the density of the graphene layer increases, PCNF must provide many active sites at the carbon end of the sidewall of PCNF for adsorption of platinum nanoparticles. there is. In addition, it is believed that carbon corrosion caused by crystallization of amorphous carbon has been resolved. In this way, PCNF, which increases the supply of silica by increasing the degree of graphitization, is suitable for fuel cells and has improved durability.
Antioxidative and Anti-Inflammatory Carbon Nanotherapy for Rheumatoid Arthritis
Authors: Choi Chanhee , Choi Yujin , Lee Sin , So Yoonhee , Kim Hongwon , Moon So-Hyun , Kim Jong-Ho
Published: December 2024

Rheumatoid arthritis (RA) is one of the most severe systemic inflammatory diseases that affect serious damage to articular cartilage, lowering the quality of life. In RA, synovium is the major site of inflammation accompanying by the severe downregulation of innate antioxidative enzymes. Hence, it would be a potential therapeutic for RA to design nanomaterial-based antioxidative nanozymes that can effectively ameliorate inflammation in microenvironment along with restoration of the innate anti-inflammatory immunity. Herein, we demonstrate a strategy to develop a carbon nanotherapeutic with antioxidative and anti-inflammatory activities by scavenging the reactive oxygen species (ROS) and reactive nitrogen species (RNS) for the treatment of RA. The nanotherapeutic carbon was synthesized through the solvothermal reaction of a condensable small organic molecule, and the synthetic process was optimized to enhance its intracellular activity. The optimized nanotherapeutic carbon exhibited superior cellular permeability and excellent intracellular antioxidative activity. The nanotherapeutic carbon could effectively eliminate intracellular ROS and RNS in vitro and in vivo through a proton transfer catalytic cycle. Additionally, the Nrf2 pathway responsible for modulating innate antioxidative and anti-inflammatory responses was upregulated after treatment with the nanotherapeutic carbon. Finally, the nanotherapeutic carbon was applied for the treatment of RA mice, showing its excellent therapeutic efficacy and distinct therapeutic pathway. The use of the biocompatible nanotherapeutic carbon can be extended for the treatment of various inflammation diseases.
Mechano-Electrochemical Energy Harvesting for Self-Powered Sensors
Authors: Choi Changsoon
Published: December 2024

Recent developments in mechano-electrochemical technology show tremendous promise for creating autonomous sensors that are instrumental in energy harvesting and health monitoring. This innovative energy conversion mechanism principally transforms the mechanical energy from stretching carbon nanotube composite fibers along their length into electrical energy. This transformation is facilitated by a combination of physical deformation and electrochemical processes.

State-of-the-art mechano-electrochemical energy harvesters are incorporating new fiber configurations, such as coiled and buckled structures made from carbon nanotubes. These fibers, when extended within an electrolyte, undergo structural modifications at the microscale, which increase the electrochemically active surface area. These modifications consequently alter capacitance and the voltage across open circuits.

The fiber described here, notable for its low Young’s modulus (0.2 MPa) and its ability to stretch up to 400%, surpasses traditional materials used for energy harvesting. It achieves a gravimetric current density of 121 A/kg and a power density of 16 W/kg through an optimal combination of macroscopic coiling and microscopic buckling. This design significantly expands the area accessible to ions, boosting electrical output.

This technology has been practically implemented in a pig bladder, proving its effectiveness as a self-powered sensor that can adaptively respond to organ volume changes. Such functionality is essential for real-time health monitoring systems, offering new ways to manage medical conditions impacting bladder functions and movements of other organs.
Nickel-Iron Interfacial Alloy Nanoparticles Encapsulated By Pyridinic-N Enriched CNT on Carbon Fiber Cloth for Bifunctional Oxygen Catalysts and Biaxially Flexible Zinc-Air Batteries
Authors: Kim Ae Rhan
Published: December 2024

Low-price, high-performance, and long-term stability electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are highly significant in the application of rechargeable zinc air batteries. In this study, we report a highly reversible bifunctional electrocatalyst for flexible Zn air batteries featuring pyridinic-N exclusively enriched carbon-nanotube-encased nickel-iron (NiFe) interfacial alloy nanoparticles derived from an LDH template on knitted carbon fiber cloth. NiFe nanoparticles are catalytically released from the NiFe-MOF to form CNT tentacles when pyrolyzed in an inert atmosphere. XPS and XAS studies revealed the dominating presence of pyridinic-N, which reduces electron localization around NiFe centers and improves the interaction with oxygenated species. As a result, the NiFe-N-CNT-KCC catalysts exhibited a low operating overpotential (η10) of 173 mV for the OER and a half-wave potential (E1/2) of 0.87 V for the ORR, superior to benchmark electrocatalysts. As an air cathode for zinc-air batteries, the NiFe-N-CNT-KCC-based battery showed excellent electrochemical performance, with an open circuit voltage (OCV) of 1.55 V, high power density (153 mW cm-2), excellent specific capacity of 793.2 mA h g-1, and long-term stability. Most impressively, the solid-state flexible zinc-air battery with the NiFe-N-CNT-KCC cathode showed admirable rate performance and exceptional mechanical stability under arbitrary bending and twisting conditions, holding great potential in practical implementation in next-generation high-power and high-energy-density batteries, even with the potential for wearable applications.
(Invited) High Temperature Effects on the Properties of Single-Chirality Carbon Nanotube Assemblies
Authors: Miyauchi Yuhei , Takakura Akira , Nishihara Taishi , Tanaka Takeshi , Kataura Hiromichi
Published: December 2024

Individual single-walled carbon nanotubes are quite thermally stable, and they exhibit narrowband thermal radiation due to sharp exciton resonance at high temperatures over 1000 K [1]. This phenomenon is expected to offer a new opportunity for utilizing exciton properties in thermophotovoltaic energy harvesting requiring excellent wavelength selective near-infrared thermal emitter [1,2]. For the realistic macroscale applications, it is necessary to utilize structure-separated single-chirality carbon nanotube assemblies that exhibit distinct exciton resonances in the optical spectra [3,4] at high temperatures. However, the effects of high temperature on the properties of high purity, single-chirality carbon nanotube assemblies have remained to be clarified. We will report on the effects of high temperature on the properties of single-chirality carbon nanotube assemblies, including the emergence of a new exciton absorption peak due to chirality-selective nanotube coalescence reactions [5].

[1] T. Nishihara, A. Takakura, Y. Miyauchi, and K. Itami, Nat. Commun. 9, 3144 (2018). [2] S. Konabe, T. Nishihara, and Y. Miyauchi, Opt. Lett. 46, 3021 (2021). [3] T. Nishihara, A. Takakura, M. Shimasaki, K. Matsuda, T. Tanaka, H. Kataura, and Y. Miyauchi, Nanophotonics 11, 1011 (2022). [4] H. Wu, T. Nishihara, A. Takakura, K. Matsuda, T. Tanaka, H. Kataura, and Y. Miyauchi, Carbon 218, 118720 (2024). [5] A. Takakura, T. Nishihara, T. Tanaka, H. Kataura, and Y. Miyauchi, submitted.
Graphdiyne-Based Two-Dimensional Nanomaterials for Next-Generation “Beyond Li-Ion” Batteries
Authors: Zheng Xueli
Published: December 2024

Two-dimensional (2D) carbon nanomaterials represent a promising avenue for the development of next-generation energy storage systems. Particularly, graphdiyne-based 2D nanomaterials have emerged as optimistic candidates due to their unique structural and electronic properties. Graphdiyne, an emerging carbon allotrope with the consolidation of diacetylenic linkages and sp2 hybridized carbon atoms, offers remarkable surface area, mechanical strength, and chemical stability. Herein, we developed a lithiophilic hydrogen substituted graphdiyne aerogel host for Li metal batteries. The hydrogen substituted graphdiyne aerogel’s lithiophilic nature and hierarchical pores drive molten Li infusion and reduce local current density within the three-dimensional host, thus achieving dendrite-free Li metal anodes. By regulating electron and ion transport within the host simultaneously, uniform lithium stripping/platting is fulfilled, thereby effectively mitigating lithium dendritic growth and enhancing lithium utilization. A symmetric cell with lithium-infused hydrogen substituted graphdiyne aerogel exhibits a low overpotential of 88 mV at 2 mA cm-2, and stable cycling of 300 cycles in carbonate electrolytes. Paired with a lithium iron phosphate cathode, a full-cell battery demonstrates excellent rate capability and long-term stability with 98.1% capacity retention after 170 cycles at 0.4 C. Moving beyond Li metal batteries, we incorporated cobalt single atom sites into hydrogen substituted graphdiyne for all-solid-state lithium-sulfur batteries. Porous hydrogen substituted graphdiyne aerogel suppressed the amount of soluble sulfur species in the solid polymer electrolytes. Furthermore, the catalytic effect of cobalt single atom sites enhanced the lithium-sulfur reaction kinetics and cycling performance of all-solid-state lithium-sulfur batteries. Our work sheds light on developing graphdiyne-based 2D nanomaterials in revolutionizing next-generation energy storage technologies and in addressing the challenges posed by the ever-increasing demand for efficient and sustainable energy storage solutions.
Evaluating Li Ion Storage Mechanism in Carbon Nanotubes (CNT) Anodes for High Energy Density Li-Ion Batteries: An Atomistic Perspective
Authors: Dive Aniruddha , Xiao Yiran , Wan Liwen , Fornasiero Francesco
Published: December 2024

Current Lithium-ion batteries (LIBs) are limited to energy densities of ~150 Wh/kg and pose safety issues associated with dendrite formation and the use of flammable liquid electrolytes that can result in the common battery failure known as thermal runaway and explosion. Lithium metal is an ideal anode for high energy density LIBs due to its high theoretical capacity (3860 mAh/g) but is dangerous due to its propensity to form dendrites. Carbon nanotubes (CNTs) with superior electronic, mechanical, and structural properties provide an exciting alternative as anode for high energy density LIBs. LIBs with vertically aligned CNTs forest help achieve the capacity retention > 80% and superior efficiency over 1000 charging-discharging cycles. However, a fundamental understanding of Li+ ion storage within CNT anodes is largely unexplored and lacking.

Experimental characterization of Li+ ion storage in CNT anodes is expensive and challenging. Previous theoretical studies have evaluated storage mechanism for isolated Li+ ions within small diameter CNTs (< 1.5 nm) forest. In common organic liquid electrolytes, Li+ ions prefer to be solvated and therefore isolated Li+ ions cannot accurately describe the Li+ storage mechanism especially in large diameter CNTs. In the current study, we carefully investigated the de-solvation mechanisms for Li+ ions in EC: EMC (3/7 w/w) 1.2 M LiPF6 liquid electrolytes both inside and outside of pristine CNT. The calculated de-solvation energies for Li+ ion adsorption onto the outside surface (~0.4-0.5 eV) of CNTs show relatively lower energies as compared to inside surface (~ 0.9-1.0 eV) of CNTs. We therefore claim that the Li+ ion storage strongly occurs on the outside surface of pristine defect-free CNTs. We further employ classical molecular dynamics simulations to investigate the Li+ ion storage on the outside of CNTs. The classical molecular dynamics simulations reveal a capacitive-type storage mechanism for pristine CNTs forest. Recent experimental reports suggest a large fraction of storage mechanism in CNT anode to be capacitive type (> 55 %) which supports the findings from atomistic modeling. Introducing structural defects (n-membered C-C rings), functional groups (-OH, =O, -COOH) etc... can lead to intercalation or plating-type Li ion storage in CNT forest which would result in higher capacity as well as energy density. However, for pristine CNTs we report the Li+ ion storage mechanism to be purely capacitive and therefore would serve as potential supercapacitor rather than battery.

This work was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
(Invited) Integrating Molecular Recognition Nanosensors with Bioprocesses for Real-Time, Non-Destructive, and Multivariate Process Analytics
Authors: Cho Sooyeon
Published: December 2024

As biological and chemical production processes become more sophisticated and evolve in various forms, there is a critical need for the development of new biochemical analysis systems capable of qualifying the versatile synthesis variables and product quality at each site. Despite traditional instrumental analyses including spectroscopy, mass spectrometry, or chromatography, being utilized as the gold standard providing precision, they are not suitable for smart process analytical technology (PAT) for future chemical and biological manufacturing, which should enable real-time, non-destructive, and on-site multivariate process monitoring without complicated sample preparations. Many optoelectronic sensors based on nanotechnology have been showing potential for this with very high sensitivity and selectivity, yet they have not been integrated into actual PAT systems due to abscence of a form factor design, sensor materials integration, and data processing techniques.

In this talk, we will introduce our recent approach on a label-free and multivariate real-time sensor system based on a unique molecular recognition array for smart biological process monitoring. We designed a wide library of 3D corona interfaces of near-Infrared (nIR) fluorescent single-walled carbon nanotube (SWCNT) transducers for the multivariate biochemical molecules as process quality attributes. We integrated this nIR fluorescent sensor array with a new mobile form factor based on microfluidics and fiber optics, and developed a remote nano-biophotonic signal transducing technique. With this, we can analyze biological production samples online, allowing for the simultaneous extraction of rich molecular data in real-time wihtout any sample preparation and labeling steps. We will introduce two representative molecular recognition based PAT systems: i) physicochemical heterogeneity analysis of therapeutic cells production for reliable treatment efficacy, and ii) Chinese hamster ovary (CHO) cell based bioreactor for a high-performance antibody production.
(Invited) Carbon/Metal Hybrid Materials for Robust Biosensors Development
Authors: Alvarez Noe T
Published: December 2024

Carbon nanotubes (CNTs) are well known for their flexibility, electrical conductivity and chemical inertness, however their use as biorecognition elements is limited due to multiple fabrication and interface aspects. Among them those related to their uniformity and stability of the CNT assemblies employed as microelectrodes. Although CNTs have shown improved detection capabilities when employed as sensors, their lack of reliable connectivity to metal surfaces has compromised their long-term performance. This talk will report fundamental calculations and experimental studies for a robust chemical bond formation of open-ended vertically oriented CNTs to copper metal surfaces. Theoretically, the nature of the bonding and the electrical resistance at the interface were determined. Experimentally, CNT bonding to metal surfaces was accomplished by grafting linker molecules to copper and gold surfaces using diazonium chemistry, for subsequent cross-linking to the proper functional groups on CNTs. These linkers were bonded to the open-ended CNTs while maintained their vertical orientation. The technique has also been applied for bonding functionalized sidewalls of CNTs to gold and other metal substrates. The application of these chemically bonded CNTs to nanostructured gold substrates as electrochemical sensors displayed high stability of the signal when exposed to oxidative conditions. Even after 540 h of exposure to a high oxidative potential, the current response remained stable, having negligible deviations between runs. Hydrogen peroxide detection using these hybrid materials involves an indirect enzyme-free oxidation mechanism, enabling their quantification at low potentials. The use of CNT/gold hybrid electrode materials allows for classifying the system as a fourth generation H2O2 sensor. Because of the low working potential, a 20-fold excess of fructose, creatinine, dopamine, uric acid, citric acid, and ascorbic acid did not interfere with hydrogen peroxide detection. Moreover, these carbon nanotube-based hybrid materials provide a large number of functionalization possibilities to employ them as electrode platforms for sensor development.
Facile Fabrication of Silicon Anodes Enhanced by Functionalized Carbon Nanotubes: Towards Affordable and High-Performance Lithium-Ion Batteries
Authors: Lee Gwanghyun , Kim Ju Yeon , Kim Dea Woo , Park Jong Hyeok
Published: December 2024

While the adoption of electric vehicles (EVs) is inevitable, the growth of the market hasn't matched predictions. Despite technological advancements improving EV competitiveness against fossil fuels, affordability remains a hurdle. Lowering the cost of lithium-ion batteries (LIBs) below that of fossil fuels is crucial for furthering vehicle electrification. Achieving this entails optimizing and simplifying the manufacturing process, given the complexity and energy intensity of LIB fabrication, which results in high costs and greenhouse gas emissions.

Recent LIB research has primarily focused on enhancing electrochemical performance, often involving complex procedures and costly materials. Silicon (Si) anodes, in particular, face challenges due to structural instability during Li alloying, requiring nanostructured particles, calcination processes, and expensive materials to improve performance. Despite Si's high theoretical capacity (~4000mAh g-1), these challenges have hindered its commercialization in LIBs. However, there's now a renewed effort among LIB manufacturers to develop high-energy-density batteries with Si anodes, prompting researchers to seek breakthrough methods to overcome Si anode weaknesses and high costs.

Carbon nanotubes (CNTs) possess unique conductive properties due to their stable one-dimensional (1D) nanostructure, making them excellent for battery electrodes. While previously expensive and limited to laboratory use, advancements in technology and market growth have led to the construction of scale-up factories, reducing CNT prices. Multi-walled carbon nanotubes (MWNTs) are particularly now affordable compared to conventional carbon black conductive materials.

Based on with this trend, we applied MWNTs to Si anodes using a simple fabrication method. Oxidized MWNTs were dispersed into an aqueous slurry without additional surfactants, enhancing electrode electrochemical behavior. MWNTs with surface oxygen groups self-arranged into interconnected network structures, forming a uniform coating on Si particles. These functionalized carbon nanotubes (FCNTs) only require a straightforward synthesis method and conventional slurry mixing process, making them ideal for large-scale production. With these advantages, FCNTs enabled superior full-cell performance with NCM cathodes.
A Breakthrough in the Efficiency and Capacity of the Dye-Sensitized Photo-Rechargeable Batteries (DSPBs) By Facilitating Redox-Driven Spontaneous Electron Transfer
Authors: Lee Myeong-Hee , Song Hyun-Kon
Published: December 2024

Faradaic redox reactions facilitating electron transfer between substances have been employed in energy devices to achieve high energy density. Many active materials capable of undergoing redox reactions can achieve higher energy density per unit volume or weight when directly immobilized onto solid substrates. However, systems such as redox flow batteries (RFBs) or dye-sensitized solar cells (DSSCs) utilize species with electrochemical activity dissolved in the electrolyte, which can limit the overall capacity of the device due to the solubility of active materials in the electrolyte. Similarly, dye-sensitized photo-rechargeable battery (DSPB) systems, which utilize dye-sensitized solar cell as a generator capable of producing electricity using light and storing it in the same device, also face the same challenge.

DSPB is a new hybrid energy system that matches the redox potentials of the mediator within the electrolyte of DSSC and storage material, enabling high energy conversion efficiency. This system not only harnesses solar energy but also enables electricity generation using indoor lighting and energy storage, allowing for the free use of stored energy. Moreover, the energy conversion efficiency using indoor lighting exceeds 13 %, showing great potential for energy recycling. In this study, we induced a potential difference between liquid and solid redox active materials, both initially possessing the same redox potential, arising from their redox reactions, facilitating the spontaneous transfer of electrons between them. This additional movement of electrons not only addressed the solubility issues of the mediator within the electrolyte, thereby increasing the device's capacity, but also improved storage efficiency during photo-charging, ultimately enhancing the overall energy efficiency. In particular, we were able to significantly improve the efficiency under solar irradiation, which typically exhibits much lower energy conversion efficiency compared to indoor lighting and is largely influenced by the kinetics of the redox mediators.

Through this strategy, the total capacity of DSPB increased by 143 % per unit volume, with an energy conversion efficiency improvement of 140 % compared to the control group under 1 SUN solar conditions, making it more efficient than any previously reported systems when utilizing DSSC as a power generation system for energy storage.
Robust 3D Lithium Cell Architecture - Inherently Boosted Safety
Authors: Prochazka Jan
Published: December 2024

The HE3DA concept of up to several millimeters thick electrodes (3D) gives lithium battery incomparable safety and brings a number of new technical attributes, which are not achievable by the existing thin film technology (2D).

3D architecture allows construction of very large cells and provides inherent safety required for large energy storage. Ceramic composite separator, together with the advanced 3D electrode design give the cell robust and stable performance, extend the temperature range, eliminate common ageing mechanisms such as active layer delamination, plastic separator shrinkage on overheating, gas bubbles or step increase of internal resistance during cycling.

Performance of 1KWh 3D cells at different load and conditions will be demonstrated.

Figure 1
(Invited) Study on the Effect of Additive in High Nickel NMC – Graphite Libs for HF- Scavenging and Stabilization of Cei Layer
Authors: Gattu Bharat , Zamani Somayeh , Atienza Dianne
Published: December 2024

Lithium ion batteries have been marked by steady progress over the past few decades owing to their high volumetric and gravimetric energy storage densities. The advent of LIBs resulted in the consistent shift of automotive industry towards hybrid EV's and BEV's. The Nissan Leaf, introduced in December 2010, became the first modern all-electric, zero tailpipe emission five door family hatchback to be produced for the mass market from a major manufacturer. Nissan has made constant efforts in improving the existing LIBs.

With the advent of new high nickel cathode materials there has been an improvement in the energy density of LIBs and the ability to internalize the material supply chain. However, these cathode materials induce additional challenges due to instability of cathode electrolyte interface and dissolution of transition metals in the systems.[1-4]

In the current work, electrolyte additive has been explored for stabilizing the cathode surface by stabilizing the cathode electrolyte interface in NMC811 and Graphite system in carbonate electrolyte system. The cycling data was analyzed with different capacity vs voltage and/current to identify the effect of additive and cycling degradation on the reaction kinetics and potentials. A methodology involving Distribution of Relaxation time (DRT) analysis, equivalent circuit design and electrochemical impedance fitting was developed to identify the different electrochemical components of the cell and their contribution towards the increase in internal resistance. The analysis was conducted during formation cycles and at different checkpoints for long cycling scenarios. The contribution of cathode and anode resistances were deconvoluted for the mixed impedance signal. Furthermore, XPS and TEM analysis were used to verify different features of the cathode and anode wherever applicable and feasible, to study the effect of the additive.

Cui, Z., & Manthiram, A. (2023). Thermal Stability and Outgassing Behaviors of High‐nickel Cathodes in Lithium‐ion Batteries. Angewandte Chemie International Edition, 62(43), e202307243.

Yu Wu, Xiang Liu, Li Wang, Xuning Feng, Dongsheng Ren, Yan Li, Xinyu Rui, Yan Wang, Xuebing Han, Gui-Liang Xu, Hewu Wang, Languang Lu, Xiangming He, Khalil Amine, Minggao Ouyang, Development of cathode-electrolyte-interphase for safer lithium batteries, Energy Storage Materials, Volume 37, 2021, Pages 77-86, ISSN 2405-8297.

Hou, J., Lu, L., Wang, L. et al. Thermal runaway of Lithium-ion batteries employing LiN(SO2F)2-based concentrated electrolytes. Nat Commun 11, 5100 (2020).

Yu Wang, Xuning Feng, Yong Peng, Fukui Zhang, Dongsheng Ren, Xiang Liu, Languang Lu, Yoshiaki Nitta, Li Wang, Minggao Ouyang, Reductive gas manipulation at early self-heating stage enables controllable battery thermal failure, Joule, Volume 6, Issue 12, 2022, Pages 2810-2820,ISSN 2542-4351.
Effective Dissolution of Tin Using Electrolytically Oxidized Alkaline Solution
Authors: Taninouchi Yu-ki , Nakano Hiroaki
Published: December 2024

Tin (Sn) is used as solder and plating in electronic devices, and its recycling is becoming increasingly important. Hydrometallurgical processes can be performed using small-scale plants without consuming large amounts of energy. Considering the strongly amphoteric nature of Sn, its dissolution (or corrosion) with alkaline solution (pH ~14) is an attractive technique for its selective extraction from various secondary resources. Sn and its alloys exhibit high corrosion resistance, and appropriate oxidants are required for their efficient dissolution. Recently, the iodate ion (IO3
−) was reported to be one of the most effective oxidants for dissolving Sn into alkaline solutions without much heating.

When Sn and its alloys are immersed in the IO3
−-containing solution, their dissolution rates decrease with increasing consumption of the oxidant (i.e., the reduction of IO3
− ions to iodide ions (I−)). To overcome this, in this study, we propose to regenerate the consumed IO3
− using electrolysis, as illustrated in Figure 1. A KI-added 1 M NaOH solution were kept in an electrolytic cell with a cation exchange membrane and then electrolyzed at ~20 °C using graphite as the anode and nickel as the cathode. After electrolysis, the concentrations of the IO3
− and I− ions in the solution were analyzed by liquid chromatography. The results showed that the I− ions can be anodically oxidized to IO3
− ions with a current efficiency of near 100%. Furthermore, when the metallic Sn samples were immersed in the anode compartment of the cell during or after electrolysis, they dissolved rapidly. The results obtained in this study indicate that the dissolution and extraction of Sn using IO3
−-containing alkaline solutions can be achieved more efficiently by combining with electrolysis.

Figure 1
Corrosion Enhanced By Hydrogenotrophic Methanogens Differently Enriched on Copper Alloys
Authors: Cazzulani Elena , Cristiani Pierangela , Chiarello Gian Luca , Franzetti Andrea
Published: December 2024

Copper and its alloys, such as brass and bronze, are widely used in heat exchangers valves, fitting, and other components of industrial facilities due to their corrosion resistance, high conductivity, and biocide properties. However, they can suffer of microbial corrosion like or more than other non-toxic materials, as several bacteria and archaea can settle and form thick biofilm on them. Nowadays, there is a growing interest in studying the metabolisms of methanogens and their effects for materials [1], due to the pivotal role that these microorganisms play in the biotechnological processes. The production of methane by CO2 and H2, for instance, is one of the most promising bioprocesses addressing the energy transition [2].

In this context, the aim of this work is to evaluate, and underline, the corrosiveness of biofilm growth on different copper alloys, starting from a common microbial pool enriched of bacteria and hydrogenotrophic archaea, treated at different temperatures and autoclaved. The study was evaluated based on 16 days test on the surface of two different copper materials, a pure Cu and a CuZn brass (40 wt. % Zn). Electrochemical investigations were performed using a three-electrode cell consisting of a working electrode (test alloy), a reference electrode (saturated Ag/AgCl electrode) and a counter electrode (titanium mesh). Investigations included open circuit potential (OCP) monitoring and electrochemical impedance spectroscopy (EIS). Chemical characterizations of the corrosion products and post-experiment observations were performed by SEM and micro-Raman spectroscopy (μRS). Molecular analysis by next generation sequencing (NGS) of 16S RNA was performed by swabbing the surface of the material and identifying the microorganisms constituting the microbial communities for each case. Results evidenced a different corrosion behavior of materials, which corresponded to different enrichment of microorganisms and different corrosion products, depending on the material and the treatment of the inoculum.

[1] Lahme S, Mand J, Longwell J, Smith R, Enning D. Severe Corrosion of Carbon Steel in Oil Field Produced Water Can Be Linked to Methanogenic Archaea Containing a Special Type of [NiFe] Hydrogenase. Appl Environ Microbiol. 2021 Jan 15;87(3)

[2] Hirano SI, Ihara S, Wakai S, Dotsuta Y, Otani K, Kitagaki T, Ueno F, Okamoto A. Novel Methanobacterium Strain Induces Severe Corrosion by Retrieving Electrons from Fe0 under a Freshwater Environment. Microorganisms. 2022 Jan 25;10(2):270.
Tuning Machine Learning Hyperparameters of a Metal-Assisted Chemical Etching (MACE) Process
Authors: St John Christopher , Arrington Christian L. , Coleman Jonathan , Risley Mason , Burckel David Bruce
Published: December 2024

Metal-assisted chemical etching (MACE or MacEtch) is a process with many confounding variables, which are covered throughout literature. In the process, a semiconductor material (typically silicon) is patterned with a metal catalyst and chemically etched in the presence of hydrofluoric acid (HF) and an oxidizing agent, typically hydrogen peroxide. The areas with metal catalyst present will form holes in the silicon, forming silicon oxide at the interface, which is then etched by the HF. The substrate material, catalyst thickness, ratio of chemistry, and geometry of features are among the variables which impact etch rate and anisotropic performance. In this work, we tune the hyperparameters of a machine learning model with the goal of better understanding the importance of the variables within the system.

SNL is managed and operated by NTESS under DOE NNSA contract DE-NA0003525

SAND2024-04792A
Insights into the Negative Impact of Carbon Binder Domains in Lithium-Ion Battery Electrode through 3D Microstructure Resolved Model
Authors: Jang Seungsoo , Kang Yejin , Park Joonam , Kim Hyeongseok , Lee Kang Taek
Published: December 2024

The lithium-ion battery (LIB) electrode consists of an active material, a conductive additive, and a binder, with the pores filled with a liquid electrolyte. The conductive additive compensates for the intrinsic low electrical conductivity of the active material, while the binder enhances mechanical bonding between components. These constituents collectively form the carbon binder domain (CBD). CBD assumes a passive role in electrochemical behavior; however, it exerts adverse effects at the microscale, obstructing Li-ion transport pathways and reducing electrochemical reaction sites. However, the heterogeneous nature of LIB electrode microstructures poses challenges for in-depth analysis. In this study, we systematically investigate the impact of CBD on LIB performance using a three-dimensional microstructure resolved model. Electrochemical modeling enables the visualization of experimentally inaccessible information, such as mass transport and electrochemical reaction characteristics. Our findings offer promising insights for advancing electrode design methodologies.
Molten Salt Corrosion Study of Alloys for Energy Application
Authors: Syed Adnan , Aria Adrianus Indrat , Nicholls John
Published: December 2024

A current challenge in concentrated solar power plants is corrosion with storing heat in molten salt to provide 24/7 renewable energy supply. This research aims to study optimisation of molten salt storage system through an understanding of the electrochemical interactions of the molten salt with the storage vessel materials. A unique facility was built to measure electrochemical performance in molten salt at high temperature with a capability of testing alloy samples. This will allow rapid performance evaluation of material and coatings in simulated high temperature service environment. Corrosion failure of these materials is associated with initiation of cracking because of electrochemical interaction between phases in the metallurgical microstructure. This can give rise to local attack, leading to crack formation and ultimately, plant failure. By using these electrochemical methods, we can better understand the corrosion mechanism.

This ongoing project enables rapid and precise evaluation of energy materials degradation by measuring jointly and in situ the electrochemical performance of sample within a molten salt as a function of temperature. The study will also be compliment using microscope study using SEM /EDX to understand the microstructural changes and XRD for corrosion products evaluation. A combination of differed salt mix at different temperature ranges will be studied in this project.
Investigation of Ruthenium and Iridium Metal as Potential Anodes for Oxide Reduction in Molten LiCl-Li2O
Authors: Moore Craig , Selmi Thomas , Chidambaram Dev
Published: December 2024

The electroreduction of UO2 during pyroprocessing is counterbalanced by the oxidation of dissolved oxygen ions typically at a platinum anode in molten LiCl-Li2O to form oxygen gas. Platinum and previously explored alternative anodes have been found to corrode concurrently with the evolution of oxygen which poses an economic challenge for implementing pyroprocessing industrially. Ruthenium and iridium metal were investigated as potential anodes for the electroreduction step of pyroprocessing. Electrochemical data for the tested anodes will be presented. Additionally, extensive surface characterization including X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy will be reported for the tested anodes.

This work was performed under ARPA-e grant DE-AR0001697. XPS was purchased under NSF MRI award 2117820. C.M. is supported by DOE Fellowship under award DE-NE0009105.
Hydrogen-Induced Electrochemical Degradation of Passive Film Formed on Ni-Ti Superelastic Alloy in an NaCl Solution
Authors: Lee Jun-Seob , Rho Seo-Young , Ando Kuga , Yokoyama Ken'ichi
Published: December 2024

This study investigated the influence of electrochemically generated hydrogen on the passivation of Ni-Ti alloy surfaces. The hydrogen charging process, conducted using galvanostatic polarization, led to an increase in the passive current density. Electrochemical Impedance Spectroscopy and Mott-Schottky analysis revealed an increase in the conductivity of the film, related to an increase in defect density following hydrogen charging. Auger electron spectroscopy reported a decrease in film thickness, and X-ray Photoelectron Spectroscopy indicated compositional changes. A critical finding was the increased electrochemical conductivity of the passive film, which can be attributed to hydrogen adsorption and/or absorption.