bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) Benefits of the Hydro to CathodeTM Li-Ion Battery Recycling Method
Authors: Gratz Eric
Published: July 2022

Battery Resourcers’ (BRs) patented Hydro to CathodeTM recycling process can accept any lithium ion battery, regardless of size, shape, or chemistry, and recover commercial quality NMC cathode powder. The reason cathode powder must be recovered for sustainable/profitable recycling is it accounts for >50% of the batteries material value. Traditional recycling process only recover the metal value which is 30% of the batteries material value. The cathode powder has been independently tested by variety of labs. NMC111, NMC 532, NMC 622 and NMC 811 have been produced to commercial quality. The Hydro to CathodeTM technology offers the ability to control composition, the particle size, tap density, and morphology of the recovered particles for either precursor or cathode materials. Thus the process is commercially viable while other processes such as direct recycling face significant challenges. This presentation discusses the benefits of the recycling process and the properties of the output material.
Circular Economy Insights: Sustainable Reuse of Aged Li-Ion LiFePO4 Cathodes within Na-Ion Cells
Authors: Gucciardi Emanuele , Galceran Montserrat , Bustinza Ainhoa , Bekaert Emilie , Casas-Cabanas Montserrat
Published: July 2022

Lithium-ion batteries (LIBs) are today considered as one of the best solutions towards an energy model based on renewable sources and zero-emission electric vehicles. However, the increased production of LIBs raises concerns regarding cost and availability of key materials such as lithium, cobalt or graphite. Indeed, after almost 20 years of cost decrease, the price of lithium-ion batteries is slowing down [1]. This is related to the fact that a lot of raw materials and metals (mainly copper, aluminum and cobalt) that are used in LiBs have increased relentlessly their prices because of its continuous demand. In this sense, are needed better performing, more price competitive and sustainable battery storage solutions beyond lithium that take into consideration the overall value chain, from access to raw material, innovative advanced materials, production, recycling and second life.

In this context, disposal and recycling are essential for the sustainability of this market and new recycling processes for LIBs are needed. Today there are processes that can recover high-value raw materials from LIBs (mainly copper, aluminum, and cobalt) but direct recycling of materials such as LiFePO4 (LFP) that has less economic value and are environmentally much more sustainable represents an economic challenge for the battery market and future research.

NaFePO4 (NFP) has been indeed proposed as one of the cheapest and most sustainable sodium-ion (Na-ion) cathode materials, [2-3] but it is not a thermodynamically stable phase and it is necessary to obtain it from LFP through redox reactions usually using expensive, toxic and hazardous reagents, cutting down its commercialization.[3-5] LFP recovering from spent LIBs can contribute to reducing the manufacturing costs of the NFP and increase the interest to recycle Li-ion batteries based on LFP cathodes.

In the perspective of a circular economy market, we propose in this work to explore the recovery of aged LFP electrodes and their reuse in new Na-ion batteries.
Recycled Graphite for Sustainable Lithium-Ion Batteries
Authors: Olutogun Mayokun , Vanderbruggen Anna , Rudolph Martin , Passerini Stefano , Bresser Dominic
Published: July 2022

Graphite – natural or synthetic – is the most dominant active material used for LIB anodes[1]. Natural graphite, however, is considered a critical material within the EU[2], while synthetic graphite is obtained from coke[3] – a carbon precursor produced from coal or petroleum. Therefore, efficient recycling and reuse of graphite are essential towards sustainability and resource preservation[4].

Herein, we report a novel and highly efficient process to recover high-quality graphite from spent LIBs. Following a comprehensive physicochemical characterization of the materials obtained, we conducted an extensive electrochemical characterization in half-cells and graphite‖NMC532 full-cells and compared the results with the data obtained for half-cells and full-cells using pristine commercial graphite. In half-cells, the recycled graphite shows remarkably high reversible specific capacities (e.g., 350 mAh g-
1 at C/20) and very stable cycling for several hundred cycles at 1C. The graphite‖NMC532 full-cells also show excellent cycling stability, with a capacity retention of 80% after about 1,000 cycles. Particularly, the comparison with the pristine graphite comprising full-cells reveals very comparable performance, highlighting the great promise of recycled and reused graphite as a pivotal step towards truly sustainable LIBs and the great goal of a circular economy.

References

[1] J. Asenbauer, T. Eisenmann, M. Kuenzel, A. Kazzazi, Z. Chen, and D. Bresser, “The success story of graphite as a lithium-ion anode material – fundamentals, remaining challenges, and recent developments including silicon (oxide) composites,” Sustain. Energy Fuels, 2020.

[2] Comisión Europea, European Commission, Report on Critical Raw Materials and the Circular Economy, 2018. 2018.

[3] S. Richard, W. Ralf, H. Gerhard, P. Tobias, and W. Martin, “Performance and cost of materials for lithium-based rechargeable automotive batteries,” Nat. Energy, vol. 3, no. Li, pp. 267–278, 2018.

[4] A. Vanderbruggen, E. Gugala, R. Blannin, K. Bachmann, R. Serna-Guerrero, and M. Rudolph, “Automated mineralogy as a novel approach for the compositional and textural characterization of spent lithium-ion batteries,” Miner.
Eng., vol. 169, p. 106924, 2021.
Direct Recycling of Cathode Active Materials from EV Li-Ion Batteries
Authors: Folayan Tinu-Ololade , Dhindsa Kulwinder , Atienza Dianne , Zhan Ruiting , Jonynas Anna , Pan Lei
Published: July 2022

Direct recycling of Li-ion batteries is a promising and low-cost recycling technology since the process recovers values of active materials directly without converting active materials into metal elements. However, the process is challenging from a separation perspective due to purity requirement. Herein, a new physical separation system was developed to recycle and produce ultra-high purity of cathode active materials from EV Li-ion batteries. Results showed that the recycled cathode active material product contained 99% purity of active materials with less than 500 ppm of aluminum and copper. Both the stoichimetry and structure of the recycled cathode active materials remained the same compared with those collected manually from electrode sheets. Results obtained from electrochemical testing showed that the capacity of the recycled materials was comparable to that of pristine cathode active materials, despite there was a lithium loss associated with battery charging and discharging. The present result demonstrates a viable direct recycling process for electric vehicle Li-ion batteries.
Prospects of Electrifying Chemical Manufacturing through Co-Conversion
Authors: Kenis Paul , Bhargava Saket
Published: July 2022

Over the next few decades the chemical industry will need to reduce drastically the greenhouse gas emissions footprint associated with the manufacturing of chemicals and fuels. Electrifying manufacturing of some intermediates or products holds promise to help meet this challenge. While techno-economic (TEA) and life-cycle (LCA) analyses of the electrochemical reduction of CO2 to products such as CO, formic acid, ethylene, and ethanol indicate their promise, these also highlight the challenge to compete in terms of cost with present day chemical conversion processes operated at scale [1].

This contribution will elaborate on the prospects of electrochemical co-conversion: performing desired chemical conversions on both electrodes of an electrolyzer. Such an electrolysis process not only uses renewable energy to produce two or more value added products simultaneously, it also avoids the energy intense oxygen evolution reaction that oftentimes is paired with CO2 reduction or hydrogen evolution (water electrolysis). Indeed, when coupled with CO2 reduction to CO, the oxygen evolution reaction on the anode consumes about 90% of the energy required to drive the overall process. Performing oxidation reactions, in particular oxidation of organic substrates, reduces the cell potential by about 0.8V, representing a reduction in overall energy consumption of 30-50%, depending on the cathode process and operating conditions. . Co-conversion electrolysis process technology could be a starting point for a new generation of chemical manufacturing technology that is significantly more energy efficient than the traditional thermochemical processes, while also able to use renewable feedstocks, such as CO2, water, biomass adducts, or organic waste streams.

This presentation will dive into technoeconomic and lifecycle analyses of a wide range of co-conversion scenarios. Using gross margin and other models, the question will be answered which electrolysis process comprised of specific combinations of cathodic reactions (CO2 reduction, hydrogen evolution, ...) and anodic reactions (various specific oxidations of organic compounds) will have the best economic prospects. Similarly, the work will provide insights as to what combinations of anodic and cathode chemical conversions are most promising from a lifecycle point of view, in reducing CO2 emissions. This work also will provide insights with respect to what factors (catalyst cost, electrode durability, ...) have the most potential in helping to further improve economic viability and to further reduce CO2 emissions.
(Invited) Using Enzymatic Bioelectrocatalysis for Nitrogen Reduction to Ammonia and Chiral Amines
Authors: Minteer Shelley D.
Published: July 2022

Enzymatic biocatalysts have been proposed for a variety of chemical manufacturing applications due to their high selectivity, but they can be utilized as electrocatalysts. This talk will discuss the "wiring" of nitrogenase (the only enzyme known to catalyze reduction of nitrogen to ammonia) to electrode surfaces for electrosynthesis. The talk will start with a discussion of nitrogenase bioelectrodes for ammonia production followed by the use of nitrogenase bioelectrodes for the selective production of chiral amines and chiral amino acids.
(Digital Presentation) 4D Printing of Inter-Crosslinking Network Structure Gel with Hinge Structure
Authors: Kameoka Masanari , Furukawa Hidemitsu , Shiblee Nahin Islam , Kawakami Masaru , Watanabe Yosuke , Khosla Ajit , Ogawa Jun
Published: July 2022

4D printing [1] is a new interdisciplinary research area made possible by the merger of scientific developments in additive manufacturing and smart materials [2]. It is a technology that allows 3D printed objects to be deformed over time by applying specific external stimuli [3] and is currently attracting attention as a technology to program biological-like movements into the internal structure of 3D printed objects. In previous research, the movement and deformation of the model has been controlled by devising the shape of the structure, such as a bilayer structure consisting of two materials with different physical properties [4]. However, it is difficult to realize the deformation in different directions simultaneously. The purpose of this research is to develop a 4D printing technology that can simultaneously deform each part of the same object in any direction.

To develop a 4D printing technology that can simultaneously deform each part of the same object in any direction, we analyzed the principle of 4D printing by swelling. We measured the swelling rate, swelling speed, compression test, and deformation amount in order to investigate the effects of material and laser irradiation frequency. As a result, it was confirmed that the swelling rate and swelling velocity increased when the amount of the initiator, TPO, was increased from a specific laser irradiation frequency. It was also confirmed that the Young's modulus increased with the increase in the number of laser irradiation. Finally, based on these results, the deformation was measured by varying the amount of initiator and the number of laser irradiations, and it was confirmed that the deformation increased with increasing the amount of initiator and the specific number of irradiations.

References

Skylar Tibbits, " 4D printing: multi-material shape change", Archit. Des. 84, 116–121 (2014). https://doi.org/10.1002/ad.1710

MD Nahin Islam Shiblee, Kumkum Ahmed, Ajit Khosla, Masaru Kawakami, Hidemitsu Furukawa, "3D printing of shape memory hydrogels with tunable mechanical properties." Soft Matter 2018, 14, 7809. https://doi.org/10.1039/C8SM01156G

Kumkum Ahmed, MD Nahin Islam Shiblee, Ajit Khosla, Larry Nagahara, Thomas Thundat, and Hidemitsu Furukawa. "Recent progresses in 4D printing of gel materials." Journal of The Electrochemical Society 167, no. 3 (2020): 037563. https://doi.org/10.1149/1945-7111/ab6e60

MD Nahin Islam Shiblee, Kumkum Ahmed, Masaru Kawakami, Hidemitsu Furukawa, "4D Printing of Shape-Memory Hydrogels for Soft-Robotic Functions." Adv. Mater. Technol. 2019, 4, 1900071. https://doi.org/10.1002/admt.201900071
(Digital Presentation) Developing Meat Alternatives with Screw-Based 3D Food Printing
Authors: Kuramochi Takaho , Kawakami Masaru , Khosla Ajit , Watanabe Yosuke , Ogawa Jun , Shiblee Nahin Islam , Furukawa Hidemitsu
Published: July 2022

Food 3D printers are next generation devices that can fabricate food products with complex internal structures and external shapes, and are expected to be used as devices for producing food products with shapes and textures that meet people's preferences, but also provide requirement of seven essential factors for a balanced diet: carbs, protein, fat, fiber, vitamins, minerals, and water [1, 2]. The food 3D printer can handle two types of food at the same time, and since it can form food in two colors, it can make food that cannot be made with a syringe nozzle. On the other hand, there are concerns about the shortage of protein supply due to the increase in population, and alternative meats that are not derived from livestock are attracting attention [3]. Currently, there are few reports of research on alternative meats using food 3D printers, and in particular, 3D modeling of alternative meat that reproduces the texture of actual meat has not been done much. In this study, we have developed a food 3D printer technology that enables the modeling of alternative meat that reproduces the texture of actual meat. We have investigated the composition of alternative meat materials suitable for 3D printing based on soy protein, and the material properties of the dough using a rheometer. In future, we will report on the movement and layering during the 3D food printing process.

References:

[1] Shunsuke Suzuki, Masaru Kawakami, Hidemitsu Furukawa, ”Food proreties suitable for 3D printer and effect on printing precsion” Materials and processing conference, 2018

[2] Suzuki, Shunsuke, Jun Ogawa, Yosuke Watanabe, MD Nahin Islam Shiblee, Ajit Khosla, Masaru Kawakami, Jun Nango, and Hidemitsu Furukawa. "Texture Control of 3D Printing: Effect of Internal Structure of 3D Printed Foods on their Fracture Process in Compression." ECS Transactions 98, no. 13 (2020): 59.

[3] Kodama, Mai, Ryo Ishigaki, Samiul Basher, Hiroyuki Sasaki, Azusa Saito, Masato Makino, Ajit Khosla, Masaru Kawakami, and Hidemitsu Furukawa. "3D printing of foods." In Nano-, Bio-, Info-Tech Sensors, and 3D Systems II, vol. 10597, p. 1059718. International Society for Optics and Photonics, 2018.
(Digital Presentation) 3D Chocolate Printing for Shape and Texture Control
Authors: Motegi Yuji , Kawakami Masaru , Watanabe Yosuke , Ogawa Jun , Khosla Ajit , Shiblee Nahin Islam , Furukawa Hidemitsu
Published: July 2022

Food 3D printing is expected to be a technology to create foods with different tastes and hardness depending on individual preferences and to solve the problem of food loss problems. In this study, we focus on the 3D printing of chocolate, whose product value is greatly affected by its appearance, entertainment and texture. Although 3D printers of chocolate are gradually appearing in the market, most of them only focus on the modeling of shape, and there are quite few printers that can form chocolate with designed texture. We develop a chocolate 3D printer using two chocolate materials. In addition to the syringe type extruder, we introduce the gear pump type extruder, which has a fine and stable extrusion. We 3d print chocolates with various internal structures using two chocolate materials and evaluate the differences in their textures by equipment measurement and by sensory tests. In addition, the melt-in-mouth feeling and the snappiness, which are important for the texture of chocolate, are investigated. In this presentation, we report the results of texture tests of black chocolate formed by a single syringe type 3D printer.

References:

Kodama, Mai, Yumiko Takita, Hideaki Tamate, Azusa Saito, Jin Gong, Masato Makino, Ajit Khosla, Masaru Kawakami, and Hidemitsu Furukawa. "Novel Soft Meals Developed by 3D Printing." Future Foods (2017): 161-181.

Suzuki, Shunsuke, Jun Ogawa, Yosuke Watanabe, MD Nahin Islam Shiblee, Ajit Khosla, Masaru Kawakami, Jun Nango, and Hidemitsu Furukawa. "Texture Control of 3D Printing: Effect of Internal Structure of 3D Printed Foods on their Fracture Process in Compression." ECS Transactions 98, no. 13 (2020): 59. https://doi.org/10.1149/09813.0059ecst

Rahman, Julkarnyne M. Habibur, MD Nahin Islam Shiblee, Kumkum Ahmed, Ajit Khosla, Masaru Kawakami, and Hidemitsu Furukawa. "Rheological and mechanical properties of edible gel materials for 3D food printing technology." Heliyon 6, no. 12 (2020): e05859. https://doi.org/10.1016/j.heliyon.2020.e05859
(Digital Presentation) Development of a Low-Torque Transfer System Using a Progressive Cavity Pumps with Gels
Authors: Sato Daisuke , Watanabe Yosuke , Ogawa Jun , Shiblee Nahin Islam , Khosla Ajit , Kawakami Masaru , Furukawa Hidemitsu
Published: July 2022

Progressive cavity pumps (PCPs) consist of a rotor and a stator. The extrusion process of PCPs is governed by a single-helical rotor which rotates eccentrically within a double-helical stator of twice the pitch length. Between the seal lines (the contact lines of rotor and stator), there are cavities which are constantly moved towards the discharge end of the pump. As one cavity is eliminated, another cavity develops, keeping the cross-sectional area of the cavities constant. The process makes a continuous non-pulsating flow in the PCPs. The developed pushing–and–suction action allows PCPs to exert significantly lower shear rates on the pumped material, compared to other pump types, such as membrane pumps or peristaltic pumps. However, the sliding of the rotor and stator in the pump causes a biting phenomenon [1-3]. Therefore, the degradation of particles in the fluid occurs. In this study, we adopted a flexible, low-friction gels as the stator material. By using gels materials as stator, we could make a pump that could discharge at low torque as previously reported by our group [4]. In this work, the rubber stator and the gels stator fabricated by 3D printing were compared and evaluated by performing discharge and torque test.

References:

[1] K. Nishimura, E. Uetsuji, and Y. Iwai, “Study on the Behavior of Particles in the Sliding Portion of a Progressive Cavity Pump”, Journal of Japanese Society of Tribologists, Vol. 63 (2018), No. 9 pp. 641-650

[2] P. Fisch, M. Holub, and M. Z. Wong, “Improved accuracy and precision of bioprinting through progressive cavity pump-controlled extrusion”, 2021 Biofabrication 13 015012

[3] M. Horie, S. Shigemitsu, S. Ookura, “Fundamental Study on Pediatric Single Eccentric Screw Blood Pump”, Turbomachinery, vol. 43(2015), No.4 pp.222-228

[4] Yeh, Yee Cheng, Naoya Yamada, Yosuke Watanabe, MD Nahin Islam Shiblee, Jun Ogawa, Ajit Khosla, Masaru Kawakami, Teruaki Akamatsu, and Hidemitsu Furukawa. “3D Printing of Soft-Matter Mono Pump in Infant Ventricular Assist Device (VAD) for Blood Pumping” ECS Transactions 98, no. 13 (2020): 31.
Flow-through Battery Electrode for Grid-Scale Energy Storage
Authors: Collins-Wildman Daniel , Higa Kenneth , Battaglia Vincent
Published: July 2022

In order to combat climate change by switching from fossil fuels to renewable sources of energy generation, there is a critical need for the development of new energy storage technologies. A robust network of energy storage facilities is essential for the stability of a grid powered primarily by wind and solar. Given the scale of the need for energy storage, it is necessary for the storage technology to be low-cost, safe, and recyclable at the end of its life. At Lawrence Berkeley National Lab, we have developed a technology capable of achieving these goals. Our system is a novel flow-battery that uses a combination of strategies to address each of the above criteria. We use an aqueous (non-flammable) electrolyte and earth-abundant materials to keep projected chemical, manufacturing, and operation costs relatively low and to reduce safety concerns. Our newly developed flow-through electrode design further reduces projected manufacturing and operation costs and simplifies material recovery/recycling. Based on our prototype, the chemical cost of storage is projected to be $59/kWh compared with $66/kWh and $154/kWh for lithium ion and vanadium redox flow batteries respectively. As energy storage facilities become larger and larger, these savings from low up-front costs and efficient recycling will become increasingly important for keeping the cost of renewable energy storage affordable.
Low-Temperature Calcination of Metal-Organic Frameworks(MOFs) to Derive the High Entropy Stabilized Oxide for High Performance Lithium-Sulfur Batteries
Authors: Raza Hassan , Cheng Junye , Chen Guohua , Guangping Zheng
Published: July 2022

Lithium-sulfur (Li-S) battery owing to high energy density and theoretical capacity is anticipated as a high-performance rechargeable power source for flexible electronic devices and electric vehicles. However, the rapid capacity fade, low Coulombic efficiency, and significant self-discharge capacity loss due to the polysulfides shuttling are the major constraints of its real-world applications. To conquer these challenges, despite the physical encapsulation of polysulfides, chemical interactions between shuttle effect-suppressive sulfur host materials and soluble lithium polysulfides have recently been emphasized. Herein, a novel approach to synthesize the high entropic stabilized oxide (HEO) at low temperature is developed from the self-sacrificing template of metal-organic frameworks (MOFs) to chemically anchor the lithium polysulfides. As-synthesized HEO850 at 850 ºC (transition temperature) exhibited a single-phase rocksalt crystalline structure with homogenous dispersion of Ni, Mg, Cu, Co, and Zn and reversible entropic phase stabilization in the certain temperature range (750-850 ºC). When employed as a chemical anchor to lithium polysulfides (LIPSs) and compared the electrochemical performance of Li-S cells with medium configurational entropic oxide (MEOs) (HEOs-one metal cation), low entropy oxide (LEOs) (HEOs-three metal cations), and routine sulfur ketjen black (S/KB) cells, it revealed a competitive reversible capacity, excellent cycling stability and a low capacity decay rate by immobilizing the LIPSs and facilitating the redox reaction in the cathode. The cells with HEO850/KB/S cathode delivered a higher initial specific discharge capacity of 1244.1 mAh g-1 than those of MEO850/S/KB (979.625 mAh g-1), LEO850/S/KB (908 mAh g-1), and S/KB (966 mAh g-1). After 800 cycles of continuous charging and discharging at 0.5 C, the capacity of 784.1 mAh g-1 with outstanding Coulombic efficiency of 99.66 % is still retained demonstrating excellent cycling stability with a negligible capacity fade rate of 0.04% per cycle. This outstanding performance could be attributed to the synergistic contribution and exposure of numerous active sites of randomly dispersed elements in the HEO850. This study not only highlights the extraordinary electrochemical performance of Li-S battery with efficient immobilization of LIPSs but also provide a novel strategy for the synthesis of HEOs at lower calcination temperature for various energy conversion and storage applications. After getting confidence with these prilimary results, Ti-based HEOs owing to both high ionic and electric conductivities will be investigated at coin and pouch cell level as future research direction.
Tunable Polarity in WSe2/TiS2 Van Der Waals Heterostructure
Authors: Lee Tae-Ju , Song Tae-Seop , Seong Tae-Yeon
Published: July 2022

Two-dimensional (2D) transition metal dichalcogenides (TMDs) formed layered van der Waals (vdW) crystals have emerged as promising candidates for varieties of potential applications, such as gas sensors, photodetectors, light-emitting diodes, Schottky diodes and memories, due to their unique physical features. However, since the existence of the metal-induced gap states (MIGS) at metal-semiconductor interfaces, it is severely difficult to adjust their electrical properties. It was demonstrated in previous researches that various metal contacts on TMDs semiconductor exhibit regular Schottky barrier height by Fermi-level pinning effect.

In this study, we suggest the van der Waals material contact between TiS2 semimetal and WSe2 semiconductor for leading van der Waals gap at their interface. Through this approach, the TiS2/WSe2 2D heterojunction can efficiently address the MIGS. Interestingly, the TiS2/WSe2 heterojunction exhibits a novel electrical transport characteristics such as distinct ambipolar and rectifying behaviors by tuning drain voltage polarity. Firstly, under reverse bias (V
ds < 0), TiS2/WSe2 heterojunction operates efficiently and allows transport of the carriers at both polarities of the gate voltage (V
bg < 0 and V
bg > 0), namely ambipolar behavior. Secondly, under the forward bias (V
ds > 0), TiS2/WSe2 heterojunction does not allow transport of the electrons at positive gate voltage (V
bg > 0), but allow transport of the holes at negative gate voltage (V
bg < 0), namely p-type behavior. To understand the carrier transport mechanism of these results, ultra-violet photoelectron spectroscopy (UPS) measurements were also carried out on the WSe2 and TiS2 flakes. It is noted that the TiS2/WSe2 junction plays a crucial role in determining a novel electronic property of this device.

Figure 1
(Digital Presentation) Thermal Runaway Initiation, Propagation and the Potential for Propagation Inhibition in Commercial Automotive Lithium-Ion Cells and Modules
Authors: Podias Andreas , Kriston Akos , Pfrang Andreas
Published: July 2022

Lithium-ion batteries, containing flammable electrolytes, have become safer in many ways since their invention. As the technology matures, energy and power densities increase: the European Council for Automotive R&D set 2030 (cell level) targets for battery electric vehicle energy density of 1000 Wh L-1, with 450 Wh kg-1 specific energy and 1800 W kg-1 peak specific power. This rise in energy and power densities increases the risk of accidental release of energy from the batteries and thermal runaway (TR). Safety is thus a key concern when designing a lithium-ion battery system for electric vehicles (EV).

TR relates to fast heating of a battery cell caused by exothermic chemical decomposition reactions of the materials inside the cells. It develops in a cell when heat is generated and cannot be dissipated quickly enough to the surroundings, giving rise to an abrupt (exponential) temperature increase and subsequent reaction rate increase. During TR, various exothermic side reactions can occur, leading to temperature increase, accompanied by pressure increase as electrolyte evaporates and venting. This can result in the emission of highly flammable gas and the formation of toxic atmosphere, as well as, in fire and, in very rare circumstances, in explosion. The corresponding temperature increase in adjacent cells (or modules) might then be sufficient to cause them to also go into TR – leading to a process known as thermal runaway propagation (TRP).

Fit-for purpose testing procedures to assess the risks associated with TRP are therefore of utmost importance and the focus should always be the safety of the EV occupants, bystanders, first responders and property. Some tests in current standards and regulations try to simulate internally driven failures (e.g. internal short circuit), but whether these tests are suitable to represent field failures remains an open question.

This work will give an insight into two selected TR initiation methods assessed within JRC’s TR initiation and propagation test campaigns, namely (a) localised rapid external heating, as developed and patented internationally by NRC (National Research Council Canada) and (b) ceramic nail penetration, as described in the IEC TR 62660-4 standard. It examines the response of short-stacks of pouch cells extracted from automotive batteries after TR is triggered in a single cell. Experimental data and analysis to better understand how TR propagates and the potential for TRP inhibition will be reported. The potential of inhibiting TRP is explored on 2- and 5-cell assemblies with a multi-layer, porous, composite insulation material between cells. Separating the cells can delay significantly TRP in adjacent cells in modules constructed with pouch cells, whereas TRP may be slowed and even inhibited as the thickness of the multilayer material varies.
(Digital Presentation) High-Resolution Imaging of Active Sites Under Reaction Conditions for Carbon-Based Electrocatalysis
Authors: Haid Richard W. , Kluge Regina M. , Schmidt Thorsten O. , Calle-Vallejo Federico , Bandarenka Aliaksandr S.
Published: July 2022

Due to the abundance and the electrochemical versatility of carbon, it is becoming an increasingly popular material for electrocatalytic applications. Whether it is used as a support material, as a catalyst, or even as a bifunctional catalyst, insights into the reaction processes are of fundamental value. In this light, we employ electrochemical scanning tunneling microscopy (EC-STM) to in-situ evaluate electrode surfaces' behavior and identify the nature of the active sites.[1] The experimental distinction between inactive and active sites of a catalytic system can be achieved by comparing the noise level of surface sites in the EC-STM signal while a reaction is ‘Off’ or ‘On’, respectively. The tunneling current will be stable under both conditions if the scanning tip is positioned over an inactive site. Over an active site, reactions occurring within the tunneling gap will influence the EC-STM signal, which can be observed as locally confined noise features superimposed on the surface morphology.

Here, we examine highly ordered pyrolytic graphite (HOPG) in alkaline and acidic media as a model system for carbon-based structures. In an alkaline medium, we compare the activity of specific surface sites under oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) conditions (Figure 1a).[2] In both cases, predominantly steps and defects are active. However, in the case of the OER, the terraces also play a role. For the hydrogen evolution reaction (HER) in acidic media, it was possible to identify individual active sites on the ‘honeycomb’ structured surface with down to atomic resolution (Figure 1b).[3] Apart from HOPG, the technique will be demonstrated for metal-organic frameworks, another class of promising catalysts for ORR and OER.

References:

[1] Pfisterer, J. H.; Liang, Y.; Schneider, O.; Bandarenka, A. S. Nature
2017, 549, 74.

[2] Haid, R. W.; Kluge, R. M.; Schmidt, T. O.; Bandarenka, A. S. Electrochim. Acta
2021, 382, 138285.

[3] Kluge, R. M.; Haid, R. W.; Stephens, I. E. L.; Calle-Vallejo, F.; Bandarenka, A. S. Phys. Chem.

Figure Caption:

Figure 1: a) n-EC-STM measurement of a step under ORR (red) and OER (green) conditions, as well as during reaction ‘Off’ (blue). The most active sites in both cases can be found at steps, indicated by the distinct noise spikes at these positions compared to reaction ‘Off’. Terraces are inactive towards the ORR. However, they do play a role in the OER.[2] © 2021 Elsevier Ltd. b) Atomically resolved active sites on HOPG under HER conditions. Bright spots in the measurements indicate active centers. They can be observed predominantly at step edges and defects, while the basal plane (terrace) remains inactive.[3]
© 2021 The Royal Society of Chemistry

Figure 1
Metal Selenide Anchored Carbon Nanotube for Boosted Oxygen Evolution Reaction
Authors: Singh Harish , Nath Manashi , Liyanage Wipula Priya Rasika
Published: July 2022

The oxygen evolution represents an important reaction in electrochemical water splitting and metal-air batteries. To deal with the increasing energy crisis and demand for sustainable clean energy, production of low-cost, high-efficiency, and robust oxygen evolution reaction (OER) electrocatalysts is urgently needed. Recently, transition metal chalcogenides (TMCs) have been used as active electrocatalysts for OER because of their high electrical conductivity and enhanced electrochemical activity. These chalcogenides based electrocatalysts show unprecedented high efficiency for OER exhibiting very low overpotentials, thereby surpassing state-of-the-art precious metal oxides or hydroxide-based catalysts. Carbon nanostructures have been shown to significantly improve their electrocatalytic performance even further. In the present work, nickel selenide nanorods (NRs) were grown inside carbon nanotubes (NiSe@CNT) through chemical vapor deposition (CVD) wherein, the carbon nanotube formed in-situ wrapping around the growing nickel selenide nanorods. Such intimate intermixing is expected to aid in rapid electron transfer from the catalyst composite and yield significantly higher current density. The encapsulation with a CNT shell can also expectedly increase stability of the selenide phase with respect to corrosion and anion leaching. Electrocatalytic behavior was explored by various electrochemical studies, including linear sweep voltammetry (LSV), chronoamperometric experiments, electrochemical surface area determination, and Tafel slope determination, under highly alkaline condition. It was observed that this NiSe@CNT composites showed enhanced electrocatalytic activity for OER. Our results indicate that the self-grown CNT around nickel selenide increases catalytic activity of this hybrid nanostructure due to an increased number of catalytic sites and electronic conductivity of the nanocomposite. The overpotential at 10 mA cm-2 for the as-synthesized NiSe@CNT catalyst is 270 mV which is much better than precious metal based electrocatalysts for OER, such as RuO2 and IrO2. In addition, the current-voltage plots were superimposable before and after 40 h of chronoamperometry test, confirming that the as-synthesized catalyst gives stable electrocatalytic OER activity in 1 M KOH medium for an extended time period. The as-synthesized catalyst was characterized by XRD, Raman spectroscopy, XPS and TEM for morphology, elemental and chemical compositions.

Keywords: oxygen evolution reaction, carbon nanotubes, In-situ wrapping

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(Invited) Understanding Chemical Doping to Improve the Thermoelectric Performance of Carbon Nanotube Networks
Authors: Ferguson Andrew , Blackburn Jeff
Published: July 2022

The thermoelectric performance of semiconductor-enriched carbon nanotube networks is intimately connected to the charge-carrier density injected into the network. This process is typically carried out by charge transfer to or from a chemical dopant, resulting in chemical counterions that reside within the network. While it is commonly accepted that the chemical structure of the dopant controls the redox properties, and therefore the ability of the dopant to modify the charge-carrier density in the carbon nanotube network, less attention is placed on the role that the residual counterion plays in the carrier transport within the doped network. We will show that the chemical structure of some novel p-type dopants based on dodecaborane clusters appended with various tunable organic moieties enables effective spatial separation of the negative counter-charge on the center of the dodecaborane cluster from the hole density injected into the carbon nanotube. This increased spatial separation, compared to more conventional oxidants like triethyloxonium hexachloroantimonate (OA) and 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), leads to a reduction in the coulombic potential barrier and improved hole transport. The enhanced transport can be attributed to reduced carrier localization, resulting in an increase in the thermoelectric power factor that surpasses the previous best-in-class for enriched semiconductor single-walled carbon nanotube thin film networks.
(Digital Presentation) Strategy to Enhance the Power Factor in Carbon Nanotubes
Authors: Yanagi Kazuhiro
Published: July 2022

Flexible thermoelectrics, which can convert waste heat into electricity at surfaces with various shapes and moving parts, is one of important techniques for efficient use of our limited energy resources. Carbon nanotubes are one of possible candidates for flexible thermoelectrics, and then we have investigated the relationships between electronic structure, location of Fermi-energy level, morphology, and thermoelectric performance of the carbon nanotubes. Particularly, we have clarified the one-dimensional characteristics in thermoelectric properties of single walled carbon nanotubes (SWCNTs). In the case of metallic SWCNTs, the thermoelectric trade-off is violated when the Fermi-energy level is tuned around van hove-singularity [1]. Thus, simultaneous enhancement of Seebeck coefficient and electrical conductivity is possible in the metallic type. In the case of semiconducting SWCNTs, we theoretically clarified that it is very difficult to identify the 1D characters in the properties of their Seebeck coefficient, power factor, and electrical conductivity. We found it is necessary to clarify the relationships between thermoelectrical conductivity (L12 term) and electrical conductivity (σ) to discuss the dimensionality in thermoelectric properties of semiconducting nanomaterials. We observed clear peak structure in the L12-σ plot in high-purity (6,5) SWCNT thin films, reflecting the 1D traces in semiconducting SWCNTs[2]. Morphology control is also important to enhance power factor of carbon nanotubes. The Seebeck coefficient does not depend on the directions of heat flow and nanotube axis, but the electrical conductivity can be enhanced when the current direction is parallel to the nanotube axis [1, 3]. On the basis of above characteristics, we determined the following strategy to enhance the power factor (PF) of SWCNTs.

Fine tuning of Fermi-energy level in the metallic type of nanotube can enhance PF

Aligned nanotubes with good electrical conductivity can enhance PF.

Thus, we started to study the thermoelectric properties of carbon nanotube fibers with extremely good electrical conductivity, which are produced by Prof. Pasquali Group in Rice Univ [4]. As a result, we found the gigantic power factor of the nanotube fiber, which is 14 mWm-1K-2, with proper Fermi-level tuning [5]. Flexible thermoelectrics with such large PF will be useful for active cooling application.

References:

[1] Ichinose et al., Nano Lett. 19, 7370 (2019) [2] Ichinose et al., Phys. Rev. Mater. 5, 025404 (2021) [3] Fukuhara et al., Appl. Phys. Lett. 113, 243105 (2018) [4] Behabtu et al., Science 339, 182 (2013) [5] Komatsu et al. , Nature Comm. 12, 4931 (2021)

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Human Hair Derived Heteroatoms Doped Porous Carbon Electrodes for Supercapacitors: Electrolytes Comparison Study
Authors: Dubey Prashant , Sundriyal Shashank , Maheshwari Priyanka
Published: July 2022

Owing to the high specific surface area, and adjustable pore size distribution, biowaste derived activated carbon (AC) has lately arouse the interest of the researchers in supercapacitor applications. Herein, we employ human hair derived heteroatoms doped porous activated carbon for supercapacitor applications. The electrochemical performance of the as produced material was evaluated in three different electrolytes: basic (6M KOH), neutral (1M Na2SO4), and acidic (1M H2SO4), with the 1M H2SO4 showing higher performance, suggesting excellent compatibility with acidic electrolyte. Surface and diffusion charge contribution examination of the AC sample in various electrolytes supports this conclusion. When compared to 6M KOH (37.5%) and 1M Na2SO4 (67.5%) electrolytes, 1M H2SO4 (79%) electrolyte exhibits better diffusion charge contribution, resulting in the maximum specific capacitance of 274 F/g at 1 A/g. Moreover, the as fabricated all-solid-state symmetric supercapacitor device delivered remarkable energy density of 47.4 Wh/kg at a power output of 1642.8 W/kg, as well as a long cycle life of 87% after 10000 charge-discharge cycles. As a consequence, this astonishing finding pave the way for the use of various biowastes for a variety of applications for energy storage.
Highly Exfoliated N-Doped Reduced Graphene Oxide Derivatives Synthesis and Application
Authors: Genorio Bostjan , Nosan Miha
Published: July 2022

Carbon-based nanomaterials such as graphene, graphene oxide, carbon nanotubes, graphene nanoribbons, etc. are considered as promising materials for energy storage and conversion, electrode sensing, optical and electronic applications. High specific surface area, porosity, and chemical modifications are some of the most important factors for tailoring the (electro)chemical, physical, and mechanical properties of graphene derivatives.1 Nitrogen-doped graphene derivatives have been identified as promising materials for energy storage and conversion2 and sensing applications. One of the most common syntheses of N-doped graphene derivatives is the N-doping of graphene oxide prepared by the Hummers method. The methods for simultaneous N-doping and reduction of graphene oxide are diverse: thermal annealing, pyrolysis, solvothermal, laser ablation, microwave-assisted, and hydrazine treatment.1 However, the above methods yield N-doped graphene derivatives, which are usually poorly exfoliated and have a low specific surface area. Therefore, an efficient strategy to improve the specific surface area of N-doped graphene oxide derivatives needs to be developed.3

Herein we present a new "induction heating method" for the preparation of N-doped reduced graphene oxide derivatives (N-rGOD) with a high specific surface area. N-rGOD was prepared in a two-step process from commercially available graphites (Gs) and multi-walled carbon nanotubes (MWCNTs). In the first step, graphite oxide precursors were synthesized from Gs or MWCNTs by the improved Hummers method. In the second step, the graphite oxide precursors were subjected to rapid heat treatment by induction heating in a reductive ammonia atmosphere. Due to the rapid thermal expansion of graphite oxide, massive exfoliation occurred to obtain N-rGOD with higher specific surface area.4 These materials were tested for energy storage and conversion applications and showed excellent properties.

References

(1) Xu, H.; Ma, L.; Jin, Z. Nitrogen-Doped Graphene: Synthesis, Characterizations and Energy Applications. J. Energy Chem.
2018, 27 (1), 146–160. https://doi.org/10.1016/j.jechem.2017.12.006.

(2) Nosan, M.; Löffler, M.; Jerman, I.; Kolar, M.; Katsounaros, I.; Genorio, B. Understanding the Oxygen Reduction Reaction Activity of Quasi-1D and 2D N-Doped Heat-Treated Graphene Oxide Catalysts with Inherent Metal Impurities. ACS Appl. Energy Mater.
2021. https://doi.org/10.1021/acsaem.1c00026.

(3) Alazmi, A.; El Tall, O.; Rasul, S.; Hedhili, M. N.; Patole, S. P.; Costa, P. M. F. J. A Process to Enhance the Specific Surface Area and Capacitance of Hydrothermally Reduced Graphene Oxide. Nanoscale
2016, 8 (41), 17782–17787. https://doi.org/10.1039/c6nr04426c.

(4) Qiu, Y.; Guo, F.; Hurt, R.; Külaots, I. Explosive Thermal Reduction of Graphene Oxide-Based Materials: Mechanism and Safety Implications. Carbon N. Y.
2014, 72, 215–223. https://doi.org/10.1016/j.carbon.2014.02.005.
Hybridization of Mesoporous Carbon and Iron Oxide for Better Mitigation of Polysulfide Shuttling in Li-S Batteries
Authors: An Meichun , Aziz Mohammad Abdul , Joo Yong Lak
Published: July 2022

With a higher theoretical capacity, lithium-sulfur (Li-S) batteries have been considered as promising candidates for next-generation batteries. Due to the non-conducting nature of sulfur, however, lithium-sulfur batteries tend to exhibit poor performance at a high current rate (C-rate).

Here we demonstrate that Fe3O4, synthesized from precursor iron (III) acetylacetonate (AAI), and mesoporous carbon material, Ketjen Black (KB), can be synergistically combined to enhance the electrochemical performance of lithium-sulfur batteries substantially. Instead of adding commercial magnetite particles into Li-S cathodes, iron oxides are synthesized and imbedded into KB from a precursor, AAI, through thermal treatments in air and Ar. The sulfur, then, is incorporated into iron oxides/KB hybrids by melting at an elevated temperature. With air-controlled electrospray as the processing method, sulfur embedded iron oxides/KB, poly(acrylic acid), and rGO sheets are mixed and directly deposited onto the carbon-coated aluminum collector, to employ as the Li-S battery cathode. X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS) studies confirm that Fe3O4 and iron carbide (Fe3C) are synthesized from the precursor, AAI, embedded in mesoporous carbon materials, and reducing the charge transfer resistance of batteries. The rate-capability tests show that systems with KB/Fe3O4 can achieve enhanced performance compared to batteries without iron oxides, especially at high C-rates. With 14 wt % of solid materials as iron oxides and iron carbide, batteries exhibit 750 mAh/g at 2C discharge/charge rates, which is 83% higher compared to systems without iron oxides. However, incorporated via 250 °C for 0.5 hr in air and 850 °C for 2 hr in Ar, the composite of KB/Fe3O4/Fe3C induces irreversible side reactions during the initial charging process, which causes a huge difference in capacity between the first and the second cycle. To achieve an optimal status with improved rate capability and acceptable initial charging time, we modify the thermal treatments and thus increase the proportion of Fe3O4 in the mixture. According to the postmortem analysis, cathodes with iron oxides can interact with soluble polysulfides strongly and alleviate the polysulfide shuttle effect significantly, compared with those without Fe3O4. Such enhanced rate capability by KB/Fe3O4 (synthesized) over KB only or KB/Fe3O4 (commercial) systems suggests that the incorporation of iron oxides can play an important role in improving the electrical conductivity of cathode and mitigating polysulfide shuttle effect.

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