bluuebunny/crossref_metadata_2025 huggingface dataset:
Development of a Controlled Humidity Differential Electrochemical Gas Monitoring System
Authors: Lee Jaeheon , McCloskey Bryan D.
Published: August 2024

Lithium-air batteries (LABs) represent a promising future battery technology due to their high energy density, although several challenges hinder them from achieving their theoretical performance. These challenges include clogging of the porous air cathode by insoluble discharge products and high overpotentials during cycling [1, 2]. A recent proposal to address these issues involves the reversible formation and oxidation of LiOH in nonaqueous LABs. Of course, LiOH-based LABs require a proton source to form LiOH from the electrochemical reaction of oxygen and lithium ions [3]; humidity in air is an obvious choice for the proton source, making the relative humidity of LAB feed gas an important parameter to control and monitor during LAB electrochemical analysis.

For LABs, galvanostatic charge/discharge coupled with quantitative gas evolution/consumption measurement is essential to understand the electrochemical processes during battery operation. Here, we report an advanced operando pressure measurement system that allows the control and monitoring of humidity in the cell headspace while also tracing overall gas consumption and evolution. Our gas handling system generates humid air using a water-containing chamber with a temperature control vessel to generate water vapor. A mass flow controller mixes dry air with humid air to generate specific relative humidity and send it to the cell. Using various low-volume in-line sensors, our system can track headspace humidity, temperature, and pressure within a custom-modified Swagelok-type cell. The total headspace volume must be small (~mL) since gas consumption occurs on a μmol scale in our lab-scale cells. To minimize headspace and dead volume within the Swagelok-type cell, a digital humidity and temperature sensor with exceptional accuracy was integrated into a customized printed circuit board (PCB). This PCB is attached to the small dead-volume Tee connection. To control the humidity inside the cell and achieve sensor data simultaneously, all sensors in the monitoring system are controlled by a LabVIEW program (National Instruments). To show the utility of this new system, we will present analyses of nonaqueous and solid-state LAB cells that operate at various humidities and current rates, while employing various known 2 e- and 4 e- oxygen reduction catalysts.

References

[1] A. C. Luntz and B. D. McCloskey, Nonaqueous Li–air batteries: a status report, Chem. Rev., 114, 11721-11750 (2014).

[2] Y. Ding, Y. Li, and Wu, Z. S, Recent advances and challenges in the design of Li–air batteries oriented solid‐state electrolytes, Battery Energy, 2, 20220014 (2023).

[3] Z. Gao, I. Temprano, J. Lei, L. Tang, J. Li, C. P. Grey, and T. Liu, Recent Progress in Developing a LiOH‐Based Reversible Nonaqueous Lithium–Air Battery, Adv. Mater., 35, 2201384 (2023).

Figure 1. Schematic diagram of the Controlled Humidity Differential Electrochemical Gas Monitoring System

Figure 1
Electrodeposited Porous Ni-Fe-Co Thin Films By Hydrogen Templating Onto an Inverted Recessed Disk Electrode
Authors: Wajdan Zahid , Podlaha Elizabeth J
Published: August 2024

Porous electrodes are advantageous for a variety of applications to enhance surface area per volume. Hydrogen templating is one well-known method to generate a porous metal, where metal deposits around generated gas bubbles from the same electrode surface. The technique has been demonstrated with noble (e.g., Au, Ag, Cu) and less noble (e.g., Ni) elemental deposits, but few alloy system.1 Ni-Fe-Co is of interest due to its electrocatalytic ability towards the oxygen evolution reaction for alkaline water splitting. Rafailović et al.2
galvanostatically electrodeposited an alloy at very high current density at pH 2 having 20 micron pore size with nano scale dendritic features, and Li and Podlaha3 potentiostatically electrodeposited Ni-Fe-Co alloys at pH < 0.5 into polycarbonate templates along with hydrogen templating to create pores in nanowires. There was a large distribution of pore size between 10 and 100 nm with the largest percentage between 20 and 40 nm. To better understand the control of pore size in the Ni-Fe-Co alloy system an inverted rotating disk electrode was used to control the limiting current of the proton reduction reaction during alloy electrodeposition. A boric acid, simple salt electrolyte was used with a three-electrode system to generate polarization curves and electrodeposits at different electrode rotation rates. The influence of mass transport and hydrogen bubble formation at different rotation rates were examined and affected porosity. Porosity was characterized by scanning electron microscopy (SEM) and the inspection of current during ferri/ferrocyanide polarization. Porous films were observed for deposits galvanostatically fabricated at current densities above the proton reduction limiting current density, but before water reduction, producing pore sizes on the order of 10s to 100s of nm, but below a micron. The ratio of the applied current density to proton reduction limiting current density was an important factor.

J. Plowman, L. A. Jones, and S. K. Bhargava, Chemical Communications, 51, 4331-4346 (2015).

D. Rafailović, C. Gammer, C. Rentenberger, T. Trišović, C. Kleber, and H. P. Karnthaler, Nano Energy, 2, 523-529 (2013).

D. Li and E. J. Podlaha, Nano Letters,
19, 3569-3574 (2019).
MnCo2O4 Spinel & Carbon Black coated Nickel Foam Electrode. A Bifunctional Water-Splitting Catalyst?
Authors: Collins Gillian , Barwa Tara N , Breslin Carmel B
Published: August 2024

Hydrogen has the potential to revolutionise how we produce and consume energy. We can meet energy demands without compromising the environment by using renewable sources such as wind, solar and wave power producing low-cost electricity to split the water molecule into its constituent parts. We could then convert Hydrogen back to electricity using a fuel cell, as illustrated in Figure 1. The by-product in this entire process is water, giving a clean technology with no toxic or greenhouses gases. Currently the best performing electrocatalytic materials for water splitting are noble metal based, namely platinum for the hydrogen evolution reaction (HER) and Ruthenium for the oxygen evolution reaction (OER). The use of these materials is unsustainable and makes fuel cells too expensive for commercial applications. We must engineer sustainable, cost-effective alternatives.

Nickel foam electrodes display desirable electrocatalytic properties such as a large surface area compared to volume with highly conducting, porous networks, while transition metal dichalcogenides show very good electronic properties with high surface areas and large active sites. In this work we show that it is possible to electrochemically and solvothermally produce CoSex and CoSex composites on a porous nickel foam electrode (NFE). The best performing materials were selected and evaluated via electrochemical impedance spectroscopy. This analysis showed high electrochemical active surface area (ECSA) values and good stability across the selected materials. Scanning electron microscopy (SEM) images reveal that the surfaces of the synthesized materials exhibit distinct morphologies and have been significantly modified. Further electrochemical evaluation of the materials reveals low overpotentials for both hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) thus showing promise as a potential bi-functional electrocatalyst in overall water splitting.

References

(1) Chaudhari, N. K.; Jin, H.; Kim, B.; Lee, K. Nanostructured Materials on 3D Nickel Foam as Electrocatalysts for Water Splitting. Nanoscale. 2017. https://doi.org/10.1039/c7nr04187j.

(2) Minadakis, M. P.; Tagmatarchis, N. Exfoliated Transition Metal Dichalcogenide-Based Electrocatalysts for Oxygen Evolution Reaction. Advanced Sustainable Systems. 2023. https://doi.org/10.1002/adsu.202300193.

(3) Sukanya, R.; da Silva Alves, D. C.; Breslin, C. B. Review—Recent Developments in the Applications of 2D Transition Metal Dichalcogenides as Electrocatalysts in the Generation of Hydrogen for Renewable Energy Conversion. J Electrochem Soc
2022, 169 (6). https://doi.org/10.1149/1945-7111/ac7172.

Figure 1
A Simple Approach for Modulating the Active Site in Fe-Based Electrocatalysts
Authors: Lee Seungmin
Published: August 2024

Proton Exchange Membrane Fuel Cells (PEMFCs) have garnered attention as a next-generation, environmentally friendly energy solution to address issues like the climate crisis and depletion of fossil fuels resulting from excessive usage. Nevertheless, the commercialization of PEMFCs faces challenges due to the use of expensive platinum catalysts for the Oxygen Reduction Reaction (ORR). In contrast, Anion Exchange Membrane Fuel Cells (AEMFCs) offer advantages by utilizing cost-effective non-platinum catalysts, making ongoing research on non-platinum catalysts for AEMFCs essential. Numerous studies have been conducted to develop M-N-C catalysts in nanoparticle units using transition metals such as Fe, Co, and Ni for AEMFCs. Notably, Fe-based catalysts with FeNx active sites are considered representative candidates for AEMFCs. Moreover, recent research aims to advance Fe catalysts by incorporating single-atom active sites to enhance mass transfer and improve reaction efficiency at the atomic level.

We have developed a straightforward method for synthesizing an Fe catalyst. The catalyst, synthesized through a redox reaction between aniline and a metal ion, followed by pyrolysis, exhibited remarkable durability and activity for the Oxygen Reduction Reaction (ORR). Notably, it possesses an active FeNx site crucial for ORR. Furthermore, by simply altering the solvent during the synthesis process, we observed a variation in the Fe-to-N ratio. Particularly noteworthy was the synthesis of Fe4N, which demonstrated activity for the Oxygen Evolution Reaction (OER). This synthesis method allows for the controlled manipulation of the catalyst's chemistry by varying the solvent, resulting in the production of Fe-based catalysts with either FeNx or Fe4N active sites, active for ORR and OER, respectively. To understand the catalyst's characteristics based on the solvent used during synthesis, we conducted a comprehensive characterization using techniques such as Thermogravimetric Analysis (TGA), X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), and Transmission Electron Microscopy (TEM). The electrochemical activity was investigated through a half-cell test, and efforts were made to interpret the results based on the catalyst's properties.
Factors Influencing Activity and Electrochemical Stability of Ru-Based Oxygen Evolution Electrocatalysts
Authors: Naymik Zachary G. , Rhodes Christopher P.
Published: August 2024

A hydrogen-based energy economy is a viable candidate to provide clean power and alleviate carbon emissions produced by hydrocarbon-based fuels. Hydrogen produced by proton exchange membrane water electrolysis (PEMWE) provides a path to clean affordable energy; however, PEMWE costs are still too high for wide-scale market adoption. Electrochemical splitting of water is energetically hindered by the oxygen evolution reaction (OER) which has sluggish kinetics, and the benchmark OER catalyst iridium oxide (IrO2) has high costs and very limited global supply. Ruthenium oxide (RuO2) provides a higher activity and lower cost compared to IrO2; however, under the high potential and highly acidic environment required for OER, RuO2 shows lower stability compared to IrO2. Our prior study demonstrated that Ti-substitution within RuO2 improved electrochemical stability, but also resulted in lower activity.1 Here, we expand our study by exploring the effects of phase, composition, surface structure, electrolyte, and operating voltage on the activity and electrochemical stability of Ru-based OER catalysts to identify key contributing factors towards improving the electrochemical stability. Catalysts materials were synthesized using wet-chemistry or high energy ball milling, and commercial materials were used for comparison and baselining. Structure was determined using X-ray diffraction, scanning electron microscopy, porosimetry measurements, and x-ray photoelectron spectroscopy. We evaluate electrochemical OER activity and stability using rotating disk electrode electrochemistry, coupled with inductive coupled plasma mass spectrometry for analysis of dissolved metals within the electrolyte. We develop structure-activity-electrochemical stability correlations to determine driving factors influencing degradation and provide a pathway to the development of materials with improved catalyst performance and lower cost.

References

Godínez-Salomón, J. F.; Ospina-Acevedo, F.; Albiter, L.; Bailey, K.O.; Naymik, Z.G.; Mendoza-Cruz, R.; Balbuena, P.B.; Rhodes, C.P., ACS Appl. Nano Mater.
2022, 5, 11752-11775.
Investigation of the Relationship between Molten Fluoride Salt Structure and Fluoroacidity Using Chromium As a Probe Redox Ion
Authors: Williams Haley , Scarlat Raluca O.
Published: August 2024

Molten fluoride salts have been studied for decades due to their applications in the production of aluminum as well as in the operation of advanced nuclear reactors. Advanced fission and fusion nuclear reactor designs may include molten fluoride salts as coolants, fuel carriers (fission), or fuel breeding blankets (fusion). Relevant to their nuclear applications are the thermophysical and thermochemical properties of the salt. These include viscosity and thermal conductivity, as well as density, vapor pressure, and heat capacity. Underlying these properties are the interactions of the ions constituting the liquid, characterized by their coordination number, correlation times, and the possible formation of polymeric networks in the melt. The composition and structure of a melt, that is, what ions are present and how they interact, dictates the macroscopic properties relevant to reactor operation. Fluoroacidity, or the activity of dissociated fluoride anions, is one metric that may be used to describe the relationship between salt chemistry and structure. Overall, understanding the relationship between molten fluoride salt chemistry and structure enables deeper understanding and, thus, prediction of property changes that may take place throughout a reactor’s lifetime.

In this poster, we present cyclic and square wave voltammetry studies of chromium speciation and diffusivity in various molten fluoride salts, connecting results with current understanding of the structure of the melts. Chromium is a thermodynamically favored corrosion product in molten salt systems, and in this study, it serves as a probe ion in different fluoride melts. Chromium trifluoride is added to various fluoride solvents and the diffusion coefficients of its various oxidation states are calculated and interpreted in light of salt structure. Experimental apparatus design and know-how for high-temperature molten salt electrochemistry are also highlighted.
Flexible Nonenzymatic Biosensor for the Detection of Glucose Using Magnetoelectrochemical Deposition
Authors: Iddirisu Desmond , Glasco Dalton Lee , Bell Jeffrey Gordon
Published: August 2024

With the continual impact of diabetes affecting more than 400 million people around the world, many researchers are continuously exploring low-cost approaches for monitoring glucose levels. By properly treating and monitoring diabetic patients we can reduce or eliminate the risk of fatal outcomes, but current glucometers focus on invasive approaches to measure glucose levels in blood. Although this is a highly effective and rapid approach, the tedious process of extracting blood or wearing an embedded devices is burdensome for many patients. Noninvasive approaches have recently begun to gain traction by monitoring glucose in sweat using flexible sensors and devices. This approach has shown promise to be an ideal alternative to commercial options for monitoring glucose levels for diabetics. Herein, we present a nonenzymatic biosensor for glucose monitoring using a flexible indium tin oxide (ITO) substrate with a copper film deposited through magnetoelectrochemical deposition. Through the incorporation of a permanent magnet, the exploration of an enhanced biosensor for glucose was performed. This magnetoelectrochemically fabricated glucose sensor was compared to a copper deposited ITO sensor fabricated without a magnet and a thorough investigation of reproducibility, sensitivity, selectivity, and stability was completed for both sensors. With the use of the magnetoelectrochemically fabricated glucose sensor, a potential noninvasive approach to detect glucose in sweat is presented with enhanced sensitivity, selectivity, and reproducibility compared to previous nonenzymatic approaches.
Matrimid/MOP-18 Derived Composite Material for High-Energy Aqueous Hybrid Supercapacitor (HSC) Electrodes
Authors: Haque Syed Fahad Bin , Balkus Kenneth , Ferraris John
Published: August 2024

The necessity for substantial advancements in electrical energy storage systems is underscored by the increasing demand driven by the extensive integration of renewable energy sources into the grid, the growing popularity of hybrid and electric vehicles, and the escalating safety requirements. Supercapacitors, characterized by their high-power density, inherently superior safety features, and longer cycle life compared to other energy storage systems, are poised to meet these escalating expectations.

In this research, an in situ dispersion of Metal-Organic Polyhedra (MOP)-18 in Matrimid is employed to construct a hybrid supercapacitor electrode with enhanced redox activity and improved electrical conductivity. A uniform solution of Matrimid and MOP-18 was electrospun, subsequently carbonized, and activated with CO2 to yield Cu/Cu2O decorated carbon fiber electrode materials. The remarkable solubility of MOP-18 was leveraged to ensure the even dispersion of nanoparticles. The thermally decomposable porous structure of MOP-18 augmented the surface area and electrolyte accessibility of the fabricated electrode. Conversely, Matrimid provided a highly conductive free-standing carbon for the electrode.

The amalgamation of these factors culminated in a notable enhancement in capacitance and energy density in a 6 M KOH electrolyte solution. The synthesized composite material achieved a peak capacitance of 253 Fg-1 and an energy density of 12.5 Whkg-1 at a current density of 1 Ag-1. The materials, methods, and techniques employed in the study can be readily scaled up industrially without significant alterations. As illustrated in the study, the use of soluble metal-organic structures to deliver redox-active materials in highly conductive carbon can result in composite electrode materials with synergistic properties.

Figure 1
Alternative Energy in Nigeria: Prospects and Limitations
Authors: Adetola Olufemi Adeyemi , Olukunle Olawale John , Agbede Bolanle Victoria , Olukunle Emmanuel Ayodeji
Published: August 2024

Energy is a major driving ingredient to the development of any country and determines the quality of life a person lives. Accessibility to constant energy supply is a major challenge in this part of the world because the demand for energy is more than the supply, and since the nation’s major source of energy is fossil fuel, it’s only an eye-opener that our overdependence on this energy source doesn’t meet the demands since energy drives forward an economy, Nigeria could as well not be developed for a couple of number of years. Alternative energy sources are examined in this review especially the renewable source of energy in Nigeria. A delve into other (alternative) sources of energy were also looked into. This review also presents the projections and limits of the alternative sources of energy in Nigeria and the way forward. Policies that can be enacted to promote the use of alternative energy were also identified and some of the limitations were stretched out. Alternative energy sources should be considered priority in the country’s agenda since more than 60% of the nation’s population has access to the national grid of which constitutes more than half of the nation’s populace.
Revitalizing Electrochemical Science and Engineering Education to Create a Clean Energy Workforce
Authors: Boettcher Shannon W. , Kempler Paul A.
Published: August 2024

Electrochemical science, engineering, and technology education and workforce development are central to the ongoing clean energy transition. In particular, I will highlight battery, hydrogen, and microelectronics industries as drivers. I then highlight a unique Electrochemistry-Technology-focused Graduate program launched through the Oregon Center for Electrochemistry in 2020. At the master’s level, the accelerated program consists of six core electrochemistry science and engineering lecture, laboratory, and project-based courses over either two or three academic quarters. In addition to core electrochemistry knowledge spanning thermodynamics, transport, kinetics, and device technology, emphasis is placed on problem solving, data analysis, programming (particularly in Python) and professional development and this additional content is embedded throughout all the core lecture and laboratory courses. Students are also introduced to continuum-level electrochemical simulations, with an emphasis on understanding the effects of boundary conditions on the simulation output. They also complete a team-based applied project sponsored by industry partners. The program ends with a nine-month paid internship leading to a master’s degree and career in the electrochemistry industry after 15 months.

The coursework is also open to PhD students and postdoctoral scholars who go on to serve as near peer mentors and teaching assistants in the program in future years, directly synergistic with their research, and building community around electrochemistry. A new BS-MS program leveraging the above has launched in 2023, allowing University of Oregon students to complete coursework for both BS and MS in just four years yielding an incredibly high return on tuition and time investment in terms of career potential and earnings. Key to the success of the programs is very low administrative overhead with technical faculty/staff leading all efforts and a transparent budget model to fund the program based on tuition return.
Molecular Insights into Redox-Active Polymer Interfaces: Solvation and Ion Valency Effects on Metal Oxyanion Selectivity
Authors: Candeago Riccardo , Wang Hanyu , Nguyen Manh-Thuong , Doucet Mathieu , Glezakou Vassiliki Alexandra , Browning Jim , Su Xiao
Published: August 2024

Chemical separations are responsible for 10-15% of the world’s energy consumption. Minimizing energy and materials inputs in selective separations is imperative for a sustainable future. Ion-electrosorption mediated by redox-active metallopolymer interfaces has the unique advantage of selectively capturing and releasing metal oxyanions in a switchable manner by adjusting the applied potential, without any regenerants. Electrosorption addresses the need for selective separation approaches with low chemical and energy inputs. Previous studies on ferrocene metallopolymers have demonstrated the role of polymer structure and applied potential on selectivity—however, the ubiquitous role of solvation in redox-polymers has remained unexplored. Here, we investigate how solvation and ion valency influence selectivity of ReO4
- vs MoO4
2- for two redox-metallopolymers, poly(vinyl ferrocene) (PVFc) and poly(3-ferrocenylpropyl methacrylamide) (PFPMAm). Both polymers display time-dependent Re/Mo selectivity, with PVFc having higher selectivity compared to PFPMAm. Operando neutron reflectometry, ellipsometry, and electrochemical quartz-crystal microbalance show that both PVFc and PFPMAm swell in the presence of ReO4
- (with PFPMAm having higher solvation), but do not swell in contact with MoO4
2-. We find that the less solvated anion (ReO4
-) is preferably adsorbed by the more hydrophobic redox-polymer (PVFc). We expect that a deeper understanding of solvation and valency effects on selectivity mechanisms in redox interfaces will expedite the development of targeted selective ion-electrosorption systems.

Figure 1
Electrochemical Recovery of Biomolecules in Redox-Mediated Electrodialysis Platform
Authors: Kim Nayeong , Lee Jiho , Jeon Jemin , Elbert Johannes , Su Xiao
Published: August 2024

In the chemical and biochemical manufacturing industry, the recovery and purification of organic species are amongst the most energy-demanding steps, due to the complexity of product streams, involving unreacted reactants, byproducts, inorganic salts along with the final products.1, 2 Membrane-integrated electrochemical methods have garnered interest as promising candidates for selective recovery of organic molecules, such as whey protein from cheese whey waste.3 Nonetheless, they still encounter a bottleneck in discriminating among charged species, primarily due to the lack of intrinsic ion selectivity on the ion-exchange membrane.1, 4 Here, we demonstrate a layer-by-layer (LBL) functionalization method to control the membrane selectivity, enabling the recovery of organic acids from a multicomponent mixture within a redox-mediated electrodialysis platform. Tailoring the physicochemical properties of ion-exchange membranes through LBL approach enables complete retention of succinate, while enhancing the overall flux for inorganic ions.1 This remarkable retention capability of the LBL membrane extends to mono- (pyruvate) and multivalent organic acids (succinate and citrate), highlighting the robustness of LBL membrane in recovering various organic species, regardless of their charges. Integration of functionalized membrane into the redox-mediated ED system facilitates the continuous enrichment of succinate with high energy efficiency and membrane stability compared to conventional electrodialysis system. Furthermore, we demonstrate continuous up-concentration of succinate in tandem with the partitioning of unreacted sugar and inorganic ions, paving the way for modular multicomponent separations in biomanufacturing processes.

References

1. Kim, N.; Lee, J.; Su, X. Precision Tuning of Highly Selective Polyelectrolyte Membranes for Redox‐Mediated Electrochemical Separation of Organic Acids. Advanced Functional Materials
2023, 33 (12), 2211645.

2. Kim, N.; Jeon, J.; Chen, R.; Su, X. Electrochemical separation of organic acids and proteins for food and biomanufacturing. Chemical Engineering Research and Design
2022, 178, 267-288.

3. Kim, N.; Jeon, J.; Elbert, J.; Kim, C.; Su, X. Redox-mediated electrochemical desalination for waste valorization in dairy production. Chemical Engineering Journal
2022, 428, 131082.

4. Kim, N.; Oh, W.; Knust, K. N.; Zazyki Galetto, F. b.; Su, X. Molecularly Selective Polymer Interfaces for Electrochemical Separations. Langmuir
2023.
Electrochemically-Driven Reversible Catch and Release of Rare Earth Elements
Authors: Sun Xiao-Guang , Ivanov Alexander , Popovs Ilja
Published: August 2024

The sustainable recovery of critical materials, such as rare earth elements (REEs), from dilute and non-traditional sources is pivotal for securing a reliable domestic supply. Using environmentally friendly methods is necessary to maximize the economic and sustainability benefits. One of the most promising approaches is the electrochemically controlled recovery of REEs, which becomes even more compelling when integrated with renewable energy sources. We developed a groundbreaking electroactive material with an exceptional affinity for REEs in their trivalent state. This material demonstrates a remarkable ability for highly reversible binding and release of REEs, controlled by the redox state of the material. We will present the REE recovery system's design principles and performance characteristics, mainly focusing on its efficacy in extracting REEs from dilute sources and structure-property relationships.
Battery Deactivation for Safe and Efficient Recycling
Authors: Mikita Riho , Suzumura Akitoshi , Kondo Hiroki
Published: August 2024

With the substantial increase in the demand for lithium-ion batteries (LIBs) for the adoption of electrification to reduce CO2 emission, safe and efficient recycling of spent LIBs is essential to utilize LIBs sustainably1. In hydrometallurgy-based or direct LIB recycling systems, which are expected to become mainstream in the future because of their low environmental impacts, deactivation is a crucial pretreatment step to safely handle LIBs during the processes2, 3. However, a common deactivation method, in which an external short circuit is induced using electronic loads or conductive liquid, cannot deactivate LIBs with disconnected electrical circuits or metallic Li plating on the negative electrode surface, despite their high safety risks.

We propose the advanced deactivation method, injecting a redox mediator (RM) solution inside the LIBs. The RM delivers electrons from the negative electrode to the positive electrode by cycling the reduction and oxidation on the negative and positive electrodes, respectively (redox shuttle reaction), resulting in discharging LIBs. In other words, the RM causes a short circuit inside the LIB. Therefore, it is possible to discharge a LIB that cannot be discharged externally, for example, a LIB with disconnected electrical circuits due to a safety device operation. Furthermore, the RM can strip Li metal plated on the negative electrode even though it is “dead lithium.” This unique characteristic contributes to the improvement in the safety and the Li collection rate in the recycling processes. Additionally, in this presentation, the deactivation mechanism of LIBs and its relationship with the electrochemical properties of the RMs will be discussed. The present findings will be beneficial and helpful for designing RMs for deactivation of more and more diversified spent LIBs.

References

J. Neumann, et al.: "Recycling of Lithium‐Ion Batteries—Current State of the Art, Circular Economy, and Next Generation Recycling" Adv. Energy Mater.
12, (2022).

A. Kwade, et al.: "Recycling of lithium-ion batteries" The LithoRec Way, Switzerland: Springler International Publishing AG (2018).

H. Rouhi, et al.: "Voltage behavior in lithium-ion batteries after electrochemical discharge and its implications on the safety of recycling processes" Journal of Energy Storage
35, (2021).
Room Temperature Efficient Regeneration of Spent LiFePO4 by Direct Chemical Lithiation
Authors: Ouaneche Tassadit , Stievano Lorenzo , Sougrati Moulay Tahar , Guery Claude , Monconduit Laure , Recham Nadir
Published: August 2024

The exponential production of lithium-ion batteries for electric vehicles (EVs) and electronic applications leads to the creation of a huge stock of batteries at the end of life. Considering the current economic, geopolitical and environmental context, the recycling of these spent batteries is becoming an urgent need in order to mitigate environmental pollution and limit the waste of valuable and critical resources1.

In this work, we report a rewarding direct recycling process of spent LiFePO4 cathode material by direct chemical lithiation in solution2. After safe opening of the spent commercial battery, a structural, morphological, spectroscopic and electrochemical characterization of the spent LFP cathode was carried out to identify the reason(s) of battery failure. The results obtained by XRD (Fig 1a) and Mössbauer spectroscopy (Fig 1b) show that the loss of lithium in the cathode (up to 50%) consumed during formation and growth of the SEI during cycling, is the major reason of the end of life of these batteries, in total agreement with the literature3.

To address the lithium shortage problem, a recycling process via direct chemical lithiation in organic solution at room temperature of the LFP cathode has been implemented. Lithium iodide (LiI) dissolved in several solvents such as acetonitrile, cyclohexane, ethanol, DMSO, methanol and propan-1,2-diol was used as both the reductant and the lithiation agent. The best results were obtained with the cathode regenerated in ethanol, which is also the most captivating and environmentally friendly solvent. The different characterizations of this regenerated cathode allow evaluating the efficiency of the regeneration process. Mössbauer spectroscopy (Fig. 2a) confirms the total reduction of FeIIIPO4 to LiFeIIPO4, while electrochemical characterization (Fig. 2b) shows encouraging properties with a reversible capacity of ~168 mAh/g for the regenerated LFP.

References:

(1) Neumann, J. et al.Recycling of Lithium‐Ion Batteries—Current State of the Art, Circular Economy, and Next Generation Recycling. Adv. Energy Mater.
12, 2102917 (2022).

(2) Ouaneche, T. et al. Room temperature efficient regeneration of spent LiFePO4 by direct chemical lithiation. 579, J. Power Sources (2023) 233248.

(3) Zhou, S. et al. Direct recovery of scrapped LiFePO4 by a green and low-cost electrochemical re-lithiation method. Green Chem.
24, 6278–6286 (2022).

Figure 1: a) XRD pattern and b) Mössbauer spectrum of the recovered LixFePO4 powder.

Figure 2: a) Mössbauer spectrum and b) Charge-discharge galvanostatic curve at C/10 of the regenerated LFP cathode as positive electrode vs. Li+/Li0 and its derivative curve.

Figure 1
Compact Energy Storage Devices Developed from Waste-Derived Electrodes via Facile Recycling Technology
Authors: Das Himadri Tanaya
Published: August 2024

Indeed, the development of sustainable and renewable energy technologies is a critical aspect of addressing the challenges posed by pollution and climate change. Electrochemical energy storage devices, such as batteries and supercapacitors, play a crucial role in this transition by enabling the efficient storage and utilization of energy. The mention of nanomaterials-based electrodes highlights a fascinating area of research and innovation. Nanomaterials offer unique properties and advantages due to their small size, high surface area, short-diffusion path, rapid kinetics, enhanced conductivity, making them highly desirable for energy storage applications.

Recycling waste to electrodes in compact energy storage device represents a particularly exciting frontier. Integrating energy storage into advance technology can enhance the portability and convenience of power sources, especially in the context of emerging technologies like wearable electronics and smart devices. However, challenges such as scalability, cost-effectiveness, and environmental impact must also be addressed to ensure the widespread adoption of these technologies. The emphasis on carbon-based nanomaterials, including graphene, carbon quantum dots, and activated carbon, as electrode materials is noteworthy. These materials show promise not only as negative electrodes but also as positive electrodes when combined with metal oxides, hydroxides, or sulphides, demonstrating their versatility in energy storage applications. Additionally, the innovative use of waste recycling, such as tires, shoots, and dry cells, for extracting carbon aligns with the broader goal of creating an eco-friendly environment. The focus on developing carbon-based electrodes from recycled waste for energy storage devices is commendable, as it not only addresses environmental concerns but also contributes to the creation of stable and efficient energy storage systems. In conclusion, this work on the generation of efficient carbon-based electrodes (graphene derived from different waste materials) for energy storage devices, showcases a multidisciplinary approach that considers both environmental sustainability and technological advancement. This research has the potential to contribute significantly to the ongoing efforts to create a more sustainable and efficient energy landscape.

Key words: Recycling, Electrochemical, Carbon, Metal oxides, Energy storage, Compact devices
Upcycling of Graphite Anodes via Tailored Solvent Treatment
Authors: Fink Kae E. , Schulze Maxwell C. , McKalip Nicholas , Verma Ankit , Berquist Zachary , Colclasure Andrew M. , Son Seoung-Bum , Ingram Brian J.
Published: August 2024

To achieve a truly closed-loop direct recycling process for lithium-ion batteries, all component materials must be recovered. To date, direct recycling method development has primarily focused on the high-value transition-metal cathode materials, while the inherently lower-value graphite has been challenging to recover in a cost-effective manner. However, end-of-life graphite contains a unique engineered value due to the presence of the solid electrolyte interphase (SEI). Growth of the SEI during the cell’s active lifetime stabilizes the electronically reactive graphite surface through an irreversible consumption of Li, and thus necessitates both excess lithiation of the cathode and a costly and time-intensive formation procedure during manufacturing. An optimized pre-formed SEI that capitalizes on existing SEI components from end-of-life batteries has the potential to significantly reduce cathode lithiation requirements and eliminate the critical bottleneck of formation cycling during cell remanufacturing. Further, retaining Li at the anode obviates the need for a separate Li leaching and recovery step, improving the overall efficiency of the direct recycling line. In this work, we present a novel approach to “upcycling” spent graphite through use of tailored chemical treatment to remove adverse (i.e., highly resistive and/or poorly passivating) SEI species while retaining beneficially passivating components. We have explored a rational set of solvents spanning a range of polarity, proticity, and molecular size to evaluate structure-property-performance relationships between applied solvent(s), removed and remaining SEI species, and electrochemical response of the resulting graphite product. Further, we have developed and optimized a robust and holistic analysis procedure that couples symmetric-cell electrochemical testing, multi-modal materials characterization, and advanced electrochemical modeling. These analysis results inform a set of correlative metrics for graphite performance relative to both solvent properties and upcycled SEI composition. We demonstrate effective tunability in the residual SEI composition by varying solvent identity and concentration, and report on several promising solvent systems that achieve comparable performance to pristine graphite.

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The Circular Path Towards Decarbonising the Li-Ion Battery Value Chain
Authors: Kallitsis Evangelos , Offer Gregory James , Edge Jacqueline
Published: August 2024

The rapid transition to clean energy and electric mobility has led to an unprecedented demand for Li-ion batteries (LIBs), necessitating a comprehensive decarbonisation of their entire value chain to meet climate goals [1]. This talk takes a holistic view at the LIB production and recycling system to explore cradle-to-cradle decarbonisation strategies. The Life Cycle Assessment (LCA) framework is used to quantify the comparative importance of developments in battery manufacturing, raw material sourcing and battery recycling in reducing greenhouse-gas emissions (GHG) arising from the globally-distributed LIB value chain.

On the upstream side, sourcing low-carbon materials is found to reduce the GHG footprint of LIB manufacturing by up to a factor of 4, depending on raw material type and source, and battery chemistry [2]. The geographical links between battery Gigafactory location and GHG emissions are also explored, revealing substantial differences between US states, Chinese provinces and European countries, traced to the carbon intensity of electricity generation [2]. On the downstream side, hydrometallurgical and pyrometallurgical treatment options for end-of-life LIBs are shown to achieve a GHG benefit of up to 40%, when recovered materials are circulated back to LIB production [3].

The battery production and recycling LCA models are integrated to present a comprehensive sensitivity analysis on the effectiveness of LIB recycling in reducing GHG emissions. This is shown to depend on battery chemistry, with lithium iron phosphate material recovery achieving lower benefits, but also on the geographical specificity of key operations, directly affecting the type of materials being displaced through secondary routes. The talk concludes with an outlook to 2035, presenting scenarios to reduce the GHG emissions of the battery value chain through technological developments, improvements in manufacturing and the establishment of circularity.

References

[1] Kallitsis, E., Lander, L., Edge, J., Bravo Diaz, L., Brown, A., Kelsall, G., Offer, G., Korre, A., 2022. Safe and sustainable lithium-ion batteries. Imperial College London-Energy Futures Lab.

[2] Kallitsis, E., Lindsay, J., Chordia, M., Wu, B., Offer, G., Edge, J. , 2023. Think global act local: the dependency of global lithium-ion battery emissions on production location and material sources. Preprint available at Research Square.

[3] Kallitsis, E., Korre, A. and Kelsall, G.H., 2022. Life cycle assessment of recycling options for automotive Li-ion battery packs. Journal of Cleaner Production, 371, p.133636.
(Invited) Recycling Zn for Rechargeable Zinc-Ion Batteries
Authors: Wang Xiaolei
Published: August 2024

Aqueous energy storage devices require highly reversible Zn electrodes, but this has been impeded by challenges including dendrite growth, low efficiency, hydrogen evolution, and metal corrosion. Here, we have successfully fabricated a reversible Zn powder electrode via engineering the growth of zinc crystals in different solvents from spent Zn foils. Theoretical calculations demonstrate that the adsorption energy gap of different solvents on the (002) or (100) facet of Zn metal varies and that a larger energy gap favors a higher orientation of Zn (002) plane. Highly oriented Zn (002) powder exhibits horizontal deposition, corrosion resistance, faster kinetics, and longer life under deep discharge (60%) in symmetric cells compared with less-oriented Zn. Under practical conditions including low N/P ratios (1–3), high-loading cathodes (10–18 mg cm−2), and lean electrolyte (5–9 μL mg−1), highly (002)-oriented Zn powder-based batteries and supercapacitors demonstrate large capacity (∼3 mAh cm−2) and energy/power density (108 Wh kg−1/2,317 W kg−1), holding promise for applications. And for the first time, we have also upcycled spent alkaline batteries into rechargeable Zn metal batteries through a simple thermal treatment of electrode waste. The regenerated Zn powder anode shows super-zincophilicity and low overpotentials even under fast rates (8 mA cm−2) and high depth-of-discharge (50 %), which can be ascribed to coating of hydroxyl-rich organic layer with abundant nucleation sites as well as high orientation of favorable (002) plane and induced horizontal plating behavior. The regenerated cathode composed of MnO2 and MnOOH manifests enhanced capacity in comparison to pristine ones. Under a low negative-to-positive capacity ratio of 3.8 and high loading of ~10 mg cm−2, the regenerated electrodes are paired to fabricate zinc metal batteries which demonstrate high energy and power densities (94 Wh kg−1, 1349 W kg−1), holding potential for practical applications. Given the sustainable, low-cost, environmental-friendly, and value-added features, the strategy proposed here will open a new pathway toward battery recycling/upcycling.
Controlling the Speciation in Electroreduction of Furanics for Production of Chemicals and Fuels
Authors: May Andrew S. , Chilunda Moses D. , Talipov Sarvarjon , Farooq Hafiz Muhammad Umar , Biddinger Elizabeth J.
Published: August 2024

There is a significant opportunity to improve the sustainability of chemical manufacturing through the pairing of biomass-derived feedstocks with renewable electricity driven processes. Furanics are promising platform chemicals that can be applied to a broad range of chemical and fuel products. Both furfural and HMF can be electrochemically reduced through hydrogenation or hydrogenolysis using copper electrocatalysts. One of the main challenges that needs to be overcome is the control of selectivity to desired products when multiple products are possible from both the electrochemistry and the homogeneous side reactions in the electrolyte. A better mechanistic understanding of the electrochemical and homogeneous reactions is necessary to enable selectivity control. Utilizing microkinetic models fed from bulk electrolysis, in situ FTIR experiments and characterization of copper electrodes after electrochemical reaction, we have been able to elucidate pH-dependent mechanisms for the electroreduction of furfural. Learnings have been extended to HMF as well.
Rhombohedral ZnIn2S4-Catalysed Anodic Direct Electrochemical Oxidative Cleavage of C-O Bond in α-O-4 Linkages in Ambient Conditions
Authors: Zhu Qi , Lam Jason Chun-Ho
Published: August 2024

The electrochemical selective oxidative transformation of biomass feedstocks into valuable oxygenated fine chemicals that are essential to the bio-commodity chemical markets. In this study, we used a rhombohedral ZnIn2S4 (R-ZIS) electrocatalyst to realise the efficient anodic cleavage of C-O bonds in benzyl phenyl ether (BPE), an α-O-4 lignin model compound, to a series of industrially relevant oxygenated mono-aromatics (benzyl alcohol, benzaldehyde, benzoic acid, etc.). In optimised conditions, the reaction achieved over 99% conversion rate with a Faraday efficiency of 51.6% that greater than most known electrocatalytic oxidative cleavage examples. The ZnIn2S4 electrocatalyst was deposited on a carbon support, and its structural properties and surface morphology were extensively investigated. Systematic chronoamperometric electrolysis coupled with18O isotopic labelling confirmed that C-O scission occurred exclusively between the benzylic carbon and phenolic oxygen. The experimental results were supported by density functional theory calculations. The substrate scoping study revealed the suitability of the R-ZIS induced electrocatalytic system for a variety of substituted lignin α-O-4 and β-O-4 model dimers. Overall, this work demonstrates an efficient anodic process that can enable the atom-efficient valorisation of lignin to produce oxygenated fine chemicals.

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