bluuebunny/crossref_metadata_2025 huggingface dataset:
Bridging the Gap between Pouch and Coin Cell Electrochemical Performance in Lithium Metal Batteries
Authors: Soulen Charles Edward , Lam Nicholas , Holoubek John , Liu Ping
Published: August 2024

In lithium metal battery research, coin cells (CC) are the most widely used laboratory instrument in academic settings. However, results thus obtained often don’t translate into pouch cell (PC) performance, which is regarded as a more reliable indicator for commercial relevance. Using both experimental and computational results, we show here that the root cause lies in the pressure distribution in these two cell formats. CCs suffer from a severe pressure inhomogeneity due to the geometry of the wave spring used to apply pressure to the cell stack. Replacing the wave spring with an elastic rubber disc applies a laterally uniform force to the cell stack, resulting in a homogeneous pressure distribution. Li || Cu half cells and Cu || LiNi0.5Mn0.3Co0.2O2 anode-free full cells using the updated structure show performance metrics on par with chemically identical PCs while traditional CCs underperform. Our solution to this common problem retains the quick, easy fabrication of CCs while producing results comparable to the PC-level.
A Novel Electrochemical Method to Detect HIV in Saliva
Authors: Saha Dipu , Botte Gerardine G
Published: August 2024

Human Immunodeficiency Virus (HIV) is a global epidemic that causes acquired immunodeficiency syndrome (AIDS) with time. Approximately 14% (one in seven) of HIV-infected people do not know their HIV status till 2022 [1]. These people have a higher chance of spreading HIV without knowing its consequences. So, there is an unmet need for more HIV testing techniques to isolate and identify all HIV-infected people as soon as after their infection. Till now, there are no available techniques to detect HIV in saliva due to HIV’s low concentrations and the inhibition properties of saliva. We developed a nickel-based electrochemical method to detect HIV in saliva for the first time. This method does not require any biorecognition element for the detection, thus making it label-free. The difference in current responses during the chronoamperometry helps to distinguish HIV from saliva. It happens due to the blocking of the formation of NiOOH in the presence of HIV on the nickel surface. This method has high sensitivity and exhibits a linear current trend with increasing concentrations of HIV culture fluid. Also, it has a lower detection limit of around 50 copies/mL and a high selectivity of HIV over Epstein-Barr Virus (EBV), which is the most common co-infection for HIV patients. Also, the most common route to transmit EBV is through saliva. So, this novel method will create a new opportunity for the commercialization of non-invasive HIV testing techniques that minimize the spreading rate of HIV by fastening HIV testing.

[1] “Global HIV & AIDS statistics — Fact sheet.” Accessed: Nov. 26, 2023. [Online]. Available: https://www.unaids.org/en/resources/fact-sheet
Course-Based Undergraduate Research Experience on the Design of Conductive Biopolymeric Nanocomposites for Enhanced Microbial Fuel Cells Performance
Authors: Gordon Chloe , Sheets Katey M , Keleher Jason J.
Published: August 2024

Microbial fuel cells (MFCs) have emerged as renewable energy sources due to their intrinsic properties to directly convert organic substrates into electrical energy. However, sub-optimal power density, limited long-term stability, and high operational costs have stunted integration at the industrial scale. These systems function through the exploitation of catalytic events of microbes under anaerobic conditions. The bacterial interactions at the electrode interface and associated electron transfer mechanisms directly impact fuel cell performance. The prominent issue is the formation of non-productive biofilms at the anode. This work focuses on the strategic design of a conductive polysaccharide-based (i.e., cellulose, agar, alginate, pectin) nanocomposite material to increase productive interactions at the anode-microbe interface. Results have shown that upon exposure to E. coli, the conducting polymer nanocomposite demonstrates enhanced current flow. Furthermore, the electrode surface was modified via non-covalent linkages of organic fuels, such as glucose, with TiO2 nanoparticles to decrease bacteria-substrate repulsions. The sugar-functionalized nanoparticle electrodes also exhibited an increased electrical response with enhanced photochemical activity. This phenomenon was observed through decreased fluorescence intensity without a decrease in cell viability and open circuit potential in the presence of light. Lastly, the “blurred” disciplinary boundaries were exploited as a model for developing an active Course-based Undergraduate Research Experience (CURE). This experience emphasized the importance of interdisciplinary problem-solving, experimental design, and the development of essential critical thinking skills.
Iron Production By Molten Sulfide Electrolysis
Authors: Suryarao Kimaya Prasad , Daehn Katrin Ellen , Allanore Antoine
Published: August 2024

With urgency and incentives to cut CO2 emissions, alongside increasing demand for steel, there is a need for technologies that use solely electricity for iron ore reduction, eliminating the role of carbon as a reductant. Herein, we propose the electrolytic production of liquid cast iron using a novel sulfide route, molten sulfide electrolysis (MSE). The process operates using sulfide chemistry and an inert anode. Sulfides are well known from non-ferrous metallurgy1 and the exclusion of oxygen supports a virtual elimination of green-house gases(GHG) emissions from the reduction step. The electrolytic decomposition of iron sulfide into iron and elemental sulfur gas operates in a multi-component molten sulfide electrolyte. The underlying thermodynamics suggests the absence of trivalent iron species (Fe3+) in such conditions, supporting the reduction of only divalent iron (Fe2+) and reducing the energy need proportionally, as compared to other oxide-based routes. Iron sulfide deposits or tailings, as well as conventional iron oxide ores after sulfidation2 are some of the suitable feedstocks for MSE.

Both thermal only, and galvanostatic electrochemical experiments were carried out on electrolyte droplets (~200mg) in a thermal imaging furnace, to confirm the electrolytic deposition of Fe and the evolution of sulfur in a 2-electrode set-up. Faradaic efficiency estimates based on mass-loss measurements – i.e. with respect to gaseous sulfur anodic evolution – are of the order of 90%. Key electrochemical attributes of MSE to be reported include impedance measurement at various fixed DC potentials, measurements at various current densities up to 2A/cm2, and the role of the total charge passed, to highlight the potential limitations observed in such an experimental set up. Characterization of the electrochemical deposits are also presented.

References:

Daehn, Katrin & Stinn, Caspar & Rush, Lucas & Benderly-Kremen, Ethan & Wagner, Mary Elizabeth & Boury, Charles & Chmielowiec, Brian & Gutierrez, Carolina & Allanore, Antoine. (2022). Liquid Copper and Iron Production from Chalcopyrite, in the Absence of Oxygen. Metals. 12. 1440. 10.3390/met12091440.

Allanore, Antoine, and Caspar R. Stinn. "Selective sulfidation and desulfidation." U.S. Patent Application 17/134,429, filed September 9, 2021.
Unlocking Value from Municipal Solid Waste Incineration Ash: Electrochemical and Chemical Approaches for Materials Recovery
Authors: Zhang Duhan , Wang Michael J. , Chiang Yet-Ming
Published: August 2024

Nowadays, in the U.S. more than 6.6 million tons of hazardous solid residue, called municipal solid waste incineration (MSWI) ash is annually generated in waste-to-energy (WTE) plants for producing electricity and reducing landfill volume. This ash cannot be further utilized for beneficial applications, so it is mostly buried and has a negative value with the cost of a disposal fee. Moreover, the economics of MSWI is challenged by the decreasing cost of renewableelectricity. However, WSWI ash represents a unique opportunity for valuable element recovery, with the embodied value ranging from $100-400/tonne. We propose an electrochemical and chemical process for mining MSWI ash that utilizes electricity from the WTE plant toelectrolytically produce acid and base streams for materials recovery and refining. We establish a sequential process of electrochemical extraction and chemical precipitation, and successfully recover Cu, Pb, Zn, Mg, Ca, Fe, Al, with a purified silica co-product. Recovery of >90% of the targeted elements at purities >90% is demonstrated. The industry-scale technoeconomic analysis shows our proposed technology will realize the possibility of extracting the embodied mineral value with net positive returns that significantly exceed the combined value of WTE electricity sales and landfilling cost.
Recycling of Waste Secondary Battery Materials to Recovery of Lithium Carbonate By Using Eco-Friendly Pyro-Metallurgical Electrolysis Process
Authors: Kwon Namhun , Lee Yongkwan , Oh Soong Ju , Kim Dong-Hyun , Sim Jae Jin , Park Kyoung-Tae , Shin Jae Hong
Published: August 2024

Recently, many types of vehicles that has been used fossil fuels energy are being replaced with EVs (Electric Vehicles) uses electrical energy. Since secondary batteries that use as the main power device of electric vehicles have a constant lifespan of 7 to 8 years, accordingly, many operating countries are constructing various plans and policies to handle with this issue. Various valuable rare metals such as nickel, cobalt, lithium, and manganese that all has limited resource, are contained in the wasted cathode material, and it could be used as a useful high-quality source if those materials can be recovered in recycle process. Thus, in this study, recover existing resources from waste cathode materials through the eco-friendly Molten Carbonate Electrolysis (MCE) process was performed. Through the process, the lithium, the main recovery target element could be recovered in the form of a compound as lithium carbonate while valuable metals such as nickel and manganese were separated and precipitated. Even though this process does not require any of acidic or organic solvent, it showed high recovery results with more environmentally friendly than the commercial hydrometallurgical recovery method while the sequence was also relatively simple. Various analysis was performed in Xray diffraction, X-ray fluorescence and FE-SEM to confirming characteristics status in recovered lithium carbonate and other precipitated powder, and thermodynamical calculation was accompanied by HSC chemistry to estimate the proper process conditions and electrode materials. In addition, through electrochemical analysis such as chronoamperometry (CA) and cyclic-voltammetry (CV), the correlation between electrode reaction tendency and lithium compound recovery rate was identified.
Lithium-Ion Battery Recycling: Ternary Deep Eutectic Solvents Enable Efficient and Selective Electrochemical Recovery of Critical Component Metals
Authors: Ashoka Sahadevan Suchithra , Usen Nazreen Mohamed Shahid , Sankarasubramanian Shrihari , Ramani Vijay K
Published: August 2024

The growing demand for lithium-ion batteries (LIBs) in electric vehicles and energy storage systems has led to a rise in LIB waste. Efficient metal recovery from LIB waste is critical to meet the growing demand sustainably. However, traditional recycling methods, such as pyrometallurgy and hydrometallurgy, have limitations regarding energy consumption, efficiency, and environmental impact. In this work, we address these challenges by exploring the potential of Deep Eutectic Solvents (DESes) as an alternative. DESes are compounds formed by mixing hydrogen bond donors and acceptors and exhibit a high capability for metal dissolution. DES has a wide electrochemical stability window (1-2 V vs Ag), making it ideal for electrodeposition. While DES holds promise for sustainable LIB recycling, current applications are hindered by high leaching temperatures (140-220°C) and prolonged durations, extending even to days.

In this study, we investigate the physical properties of a novel ternary DES and assess its leaching capabilities alongside electrodeposition studies. The leaching efficiency (LE) of metals using ternary DES is compared to the binary DES, composed of choline chloride and ethylene glycol (1:2 ChCl: EG). For the same leaching conditions (900C, 24 hr), the leaching efficiency (LE) of metals using binary DES, is 20%, whereas the LE of metals from ternary DES is nearly 100%. We optimized the leaching conditions and investigated the leaching kinetics. The electrochemical properties of the tailored, ternary DES are explored, revealing an electrochemical window of 2-3 V vs Ag. We analyze current density–time transients using the Scharifker–Hills model for instantaneous and progressive nucleation to study the early nucleation and growth mechanism of electrodeposition. Furthermore, we perform potentiostatic electrodeposition of metals from the leach liquor on different substrates, such as copper sheet and carbon at various constant potentials (-0.7 V to -1 V vs Ag). The effect of applied potential, stability of working and counter electrodes, and growth mechanism of deposited metals are studied. The electrodeposited metals are characterized using scanning electron microscopy with energy-dispersive X-ray spectroscopy and X-ray diffraction techniques. Our findings indicate that the proposed ternary DES holds significant promise for efficient and environmentally friendly metal recovery from LIB waste, paving the way for advancements in sustainable battery recycling technologies.

Figure 1
Recycling Process of Spent Alkaline and Zn-C Batteries for the Re-Utilization in Rechargeable Zn-Ion Battery
Authors: Pornprasertsuk Rojana , Qin Jiaqian , Kasemchainan Jitti , Kheawhom Soorathep , Tantavitchet Nisit , Thamyongkit Patchanita , Cheacharoen Rongrong , Somwangthanaroj Anongnat , Manowilaikun Kamonpan , Yoaharee Keeratipron , Thongsri Auscha , Waikhani Chaithawat , Kanthawong Budsayamas , Tankam Threeranon
Published: August 2024

The Zn, Mn and C extraction processes from spent primary batteries and the synthesis of recycled Zn film, MnO2 and MnO2/C for Zn-ion battery application were developed in the project. The Zn, Mn and C extraction process involved the acid leaching of Zn and Mn ions from the spent alkaline and Zn-C battery electrodes in the lab-scale was initially investigated using various leaching conditions. The acid leaching using 0.5-2 M HCl and H2SO4 at ambient temperature providing Zn extraction efficiencies in a range of 72.3-95.3%. By introducing an inexpensive reducing agent namely sodium sulfide (Na2S), sodium metabisulfite (Na2S2O5) or hydrogen peroxide (H2O2) in 2M H2SO4, the Mn extraction efficiency for Mn was increased from 21.9% (with no reducing agent) up to 48.4%, 82.8% and 98.9%, respectively. The upscale leaching study was subsequently performed in a 100-L pilot scale reactor demonstrated the Zn and Mn extraction efficiencies of 71% and 65%, respectively. Using the leaching solutions from the upscale hydrometallurgical route, Zn-film fabrication via electrodeposition process, and the MnO2 and MnO2/C synthesis via hydrothermal techniques were performed. Additionally, the one-step synthesis of MnO2/C via one-step hydrothermal method with no acid leaching was also explored in this study. The recycled Zn, MnO2, MnO2/C and C residual were subsequently used as the anode and cathode main components in the CR2032 and pouch-cell rechargeable Zn-ion batteries. The recycled MnO2 and MnO2/C provided similar performance as the commercial products, which indicating the recycled MnO2, MnO2/C could be effectively utilized in the Zn-ion battery, while the utilization of recycled Zn-film provided slightly lower performance compared to that of the commercial Zn foil.
(Invited) Electrochemical Engineering Approaches for High-Performing Electrosynthesis of Polymer Precursors
Authors: Modestino Miguel A
Published: August 2024

The chemical industry accounts for ~5% of the US energy utilization and >30% of the US energy-derived industrial CO2 emissions. Amongst these processes, the production of organic chemical commodities, many of which are used as polymer precursors, account for the majority of the energy utilization (>1200 TBTU/y). The electrification of these processes via the implementation of electro-organic reactions could accelerate the decarbonization of the chemical industry, and bring additional sustainability advantages over their thermo-chemical counterparts. Currently, however, two major challenges prevent the deployment of electro-organic reactions: their low selectivity and their low production rates. To circumvent these barriers, our group deploys electrochemical reaction engineering principles to engineer electrode/electrolyte interfaces and design high-performing electro-organic processes. In this presentation, I will discuss how we implement this approach to understand and improve the performance of electro-organic reactions for the production of large-scale precursors for the production of Nylon 6,6 and polyethylene.

The production of Nylon 6,6 involves the step-growth polymerization of 1,6-hexanediamine (HMDA) with adipic acid. HMDA is currently produced by the hydrogenation of adiponitrile (ADN). Here, I will present our insights into the electrohydrodimerization of acrylonitrile (AN) to adiponitrile (ADN). This is one of the largest electro-organic reaction deployed in industry and serves as a model process for the development of practical organic electrochemical processes. Our investigations on ADN uncovered relationships between the microenvironment at and near the electrical double layer (EDL) and reaction performance metrics (i.e., selectivity, efficiency, and productivity). I will discuss general guidelines for electrolyte formulation, dynamic electrochemical operation, the implementation of convective forces to mitigate transport limitations, ultimately leading in the conversion of AN to ADN at Faradaic efficiencies >80% and current densities of 100’s mA/cm2. Our learnings on ADN electrosynthesis helped us to engineer the electrocatalytic hydrogenation of ADN to HMDA, achieving the highest reported selectivity to date for this reaction (>95%). I will also show how similar electrochemical engineering approaches allowed us to elucidate factors that control performance in the electrochemical production of ADN from glutamic acid, an abundant and inexpensive bio-based feedstock, and of ethylene from bio-derived propionic acid. Through our studies, we aim to electrify and bring sustainability to chemical manufacturing, one reaction at a time.
One-Pot Electrosynthesis of Gamma-Butyrolactone (GBL) from Furoic Acid
Authors: Liu Shengqin , Lam Jason Chun-Ho
Published: August 2024

The catalytic valorization of biomass to afford synthetically useful small molecules is essential for sustainable biorefinery processes. Herein, we present a mild cascaded electrochemical protocol for converting furoic acid (FA), a common biomass-derived feedstock, into a versatile platform chemical, gamma-butyrolactone (GBL). All involved species participate in the desired redox pathway with high selectivity: FA was electrochemically oxidized with 84.2% selectivity to 2(5H)-furanone (2-FO), the olefin of which was then hydrogenated to yield GBL with 98.5% selectivity. We identified that a certain temperature is an important factor in enabling the one-pot reaction as it promotes thermal desorption of the key intermediate. The reaction was scalable to gram-scale, producing high-purity GBL isolated through a simple solvent extraction from a 500-mL electrolysis scale reaction.
Electrocatalytic Reduction of Oxygen to Peroxide on a Microporous Carbon Layer in a Gas Diffusion Electrode: Implications for Scale-up
Authors: Bashir Shahid M. , Gyenge Elod L.
Published: August 2024

When coupled with renewables, the two-electron oxygen reduction reaction(O2RR) could be a valuable process to generate hydrogen peroxide (H2O2), a versatile and environmentally friendly oxidant[1]. While the electrocatalyst's nature determines the catalytic activity and selectivity (2e- vs. 4e- reduction), the O2 gas mass transport, electrolyte type (e.g., alkaline, neutral, or acidic) and its flow rate, and the electrode configuration (e.g., trickle-bed or gas diffusion (GDE) electrode) are also essential factors for scale-up[2-4]. Typically, operational current densities for O2RR are limited to less than 100 mA cm-2, which is inadequate for industrial applications. The porous gas diffusion electrode (GDE) assembly provides continuous O2 gas delivery at the catalyst/electrolyte interface by overcoming O2 mass transport limitations encountered in trickle-bed or dissolved gas (single-phase) configurations. While the GDE could enable the operation under industrially relevant current densities (i.e., > 100 mA cm-2), for two-phase flow processes, flooding imposes severe challenges in the GDE scale-up and the durability of the process. Here, we present that a microporous carbon-coated gas diffusion electrode could enable very high current density (> 500 mA cm-2) synthesis of alkaline peroxide in a flow reactor with more than 90% faradaic efficiency. The microporous carbon layer provides dual functionality, namely the catalytically active sites for the reaction and controlling the GDE flooding. In addition to the electrode design, the two-phase fluid flow dynamics and electrolyzer operation conditions are significant factors for long-term stability. Although the fluid flow effect on the trickle bed type electrolyzer has been studied [3], no study exists on the systematic investigation of the two-phase mass transfer effect in the GDE-based electrolyzer for peroxide generation with a catholyte layer. The experimental findings and mass transfer modeling highlight further improvements concerning the process scale-up.

References

[1] N. Wang, S. Ma, P.Zuo, J. Duan and B. Hou, Adv. Sci., 2021, 8(15), e2100076-e2100076

[2] E. L. Gyenge and C. W. Oloman, J. Electrochem. Soc., 2005, 152(3), D42-D53

[3] I. Hodgson and C. Oloman, Chem. Eng. Sci., 1999, 54(23), 5777-5786

[4] Q. Zhang, M. Zhou, G. Ren, Y. Li and X. Du, Nat. Commun., 2020, 11(1), 1731
Enhancing Efficiency and Selectivity of Electrochemical Regeneration of NADH By Dynamic Operation
Authors: Al-Shaibani Mohammed Ali Saif , Sakoleva Thaleia , Zivkovic Luka A. , Dörr Mark , Bornscheuer Uwe , Vidakovic-Koch Tanja
Published: August 2024

The demand for the reduced nicotinamide adenine dinucleotide (1,4-NADH) and reduced nicotinamide adenine dinucleotide phosphate 1,4-NAD(P)H in industrial processes, particularly in the pharmaceutical sector, necessitates their continuous regeneration to mitigate cost implications [1]. In this respect, direct electrochemical cofactor regeneration is a promising alternative, but challenges in achieving optimal selectivity have hindered its widespread industrial integration.

This study focuses on advancing the efficiency and selectivity of electrochemical NADH regeneration through dynamic potential inputs, inspired by recent findings demonstrating improved selectivity using dynamic potential inputs instead of steady-state conditions [2]. Various dynamic, pulsed potential profiles are tested and compared with steady-state conditions, revealing distinct advantages in selectivity. Nicotinamide adenine dinucleotide reduction reaction is then coupled with the enzymatic conversion of a substrate (cyclohexenone) to a product (cyclohexanone). In this electroenzymatic biotransformation, 1,4-NADH formed electrochemically is utilized as a second substrate of enzyme enoate reductase. The success of this coupling is evident in the observed formation of the desired product. This research not only contributes to the fundamental understanding of electrochemical co-factor regeneration but also demonstrates its practical application. By combining the advantages of electrochemical and enzymatic reactions, we pave the way for more sustainable and economically viable industrial processes. The presented results mark a significant step towards harnessing the full potential of electrochemical regeneration in facilitating enzymatic transformations with enhanced efficiency and selectivity through a pulsed dynamic operation.

References

1. Wu, S., et al., Biocatalysis: Enzymatic Synthesis for Industrial Applications. Angewandte Chemie International Edition, 2021. 60(1): p. 88–119.

2. Miličić, T., et al., Pulsed electrolysis – explained. Faraday Discussions, 2023. 246(0): p. 179–197.
Chlor-Iron Process for the Low-Temperature, Direct Reduction of Iron Oxide for Green Steel
Authors: Kempler Paul A. , Konovalova Anastasiia , Noble Berkeley B.
Published: August 2024

The reduction of iron ores to metal for steelmaking produces comparable carbon emissions to all light-duty vehicles. We have identified a scalable electrochemical pathway for iron (Fe) production, which we term the chlor-iron process, that consumes only iron and salt water as reactants and could potentially be cost-competitive with iron produced in blast furnaces. Here, we report recent investigations on the mechanism of direct oxide reduction using naturally occurring and synthetic ores and identify key impurities that influence the current efficiency towards Fe. We present device-level data for continuous production of Fe and Cl2 at cell efficiencies < 5 MWh per tonne and with repeated harvesting of iron combined with technoeconomic analysis of pathways to cost competitive iron production. Lastly, we share ongoing scale-up efforts including recent data from a 100 cm2 bifacial cell. The process is unique in that the co-production of NaOH can lead to a net-negative emissions pathways for metals production.
Development of High-Performance Bipolar Membranes with Optimal Junction Properties for Efficient Electro-Membrane Processes
Authors: Song Hyeon-Bee , Lee Ji-Min , Kang Moon-Sung
Published: August 2024

A bipolar membrane (BPM) is a special type of ion-exchange membrane in which an anion-exchange layer (AEL) and a cation-exchange layer (CEL) are combined. Water molecules can be easily dissociated at the interface of the BPM by the strong electric field generated when a reverse bias voltage is applied through the membrane. Such dissociation leads to the generation of proton and hydroxide ions, which are then transported through the CEL and AEL, respectively, resulting in the production of acid and base solutions. Under a forward bias, these ions are drawn back to the bipolar interface, where they neutralize each other. The energy derived from this neutralization process, represented as a junction potential (JP) value, is a key factor in the BPM's efficiency. BPMs with ideal JP values are critical for achieving high separation and energy efficiencies in electro-membrane processes. Furthermore, for the prolonged operation of these processes, BPMs must possess a highly adhesive bipolar junction. Our work includes the development of a novel BPM with an ideal JP and a highly adhesive bipolar junction. This BPM has been applied to various electro-membrane processes, including an acid-base flow battery and direct seawater electrolysis. The BPMs are fabricated using poly(phenylene oxide) (PPO)-based ionomers, and incorporates an iron-based catalyst and a reinforcing material. These additions enhance the water-splitting performance and the durability of the interface between the ion-exchange layers. The prepared BPMs not only demonstrated excellent interfacial adhesiveness and mechanical properties but also achieved a water-splitting efficiency of 98% or higher. In comparison to commercial BPM, the electro-membrane processes utilizing the prepared BPM exhibited superior performance. This work was supported by the National Research Foundation of Korea (NRF) grants funded by the Korean government (MEST) (NRF-2022M3C1A3081178 & NRF-2022M3H4A4097521).
Re-Functionalization of Aged Lithium Iron Phosphate Cathode Materials
Authors: Gee Carol-Lynn , Amador Carolyn , Nesvaderani Farhang , Hadidi Lida , Gates Byron D.
Published: August 2024

As lithium-ion batteries continue to be implemented in everyday technologies, it is imperative to repurpose these battery materials upon their degradation. Carbon-coated lithium iron phosphate (LFP/C) is considered one of the most stable cathode materials for application in lithium-ion batteries. Due to this stability, LFP/C possesses a remarkably long cycle life of greater than 3000 cycles.1 Extended cycling of these cathode materials may result in multiple modes of degradation, including degradation of the carbon coating, and loss of contact between the cathode and the current collector.2,3 In this work, a suitable process and reagents have been selected to isolate and purify the LFP/C from the cathodes of cycled batteries. Isolating and purifying aged LFP/C materials enables the diagnosis of the mode(s) of degradation of these materials and their coatings using a variety of techniques including X-ray diffraction, scanning electron microscopy, and transmission electron microscopy methods.

Furthermore, additional work was pursued to give new life to these isolated, spent cathode materials. The addition of a coating with a relatively high lithium conductivity to the aged LFP/C particles was sought to provide a second life to these electrochemically aged materials. Half-cells were fabricated using the coated, aged LFP/C cathode materials to compare their performance to both pristine LFP/C nanoparticles and aged LFP/C nanoparticles without the addition of this custom coating. Electrochemical testing techniques such as galvanostatic cycling, cyclic voltammetry, and electrochemical impendence spectroscopy were used to probe the performance of each type of LFP/C nanoparticle as cathode materials in lithium-ion batteries. The coated, aged LFP/C particles were also characterized using transmission electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy techniques. The techniques developed herein can be used to isolate, purify, and re-functionalize other cathode materials from lithium-ion batteries.

Lewerenz, M.; Munnix, J.; Schmalstieg, J.; Kabitz, S.; Knips, M.; Sauer, D. U. Systematic aging of commercial LiFePO4|Graphite cylindrical cells including a theory explaining rise of capacity during aging. Power Sources.
2017, 345, 254-263.

Wang, L.; Qiu, J.; Wang, X.; Chen, L.; Cao, G.; Wang, J.; Zhang, H.; He, X. Insights for understanding multiscale degradation of LiFePO4 cathodes. eScience
2022, 2(2), 125-137.
KxFeO2 As Electrode Material for K-Ion Batteries
Authors: Sagot Armance , Kovrugin Vadim , Stievano Lorenzo , Pralong Valerie
Published: August 2024

To meet future energy demands, developing beyond-lithium energy storage technologies have become a major part of global research activities. Potassium-ion batteries (KIBs) represent a promising technology thanks to their chemical and economic advantages1–3. The majority of the work on layered transition oxide was done on the KxMnO2 family4,5 due to their safety and price advantage.

Interestingly, KFeO2 structure is not a layered structure as for LiFeO2 or NaFeO2; this structure is defined as FeO4 tetrahedral linked by their corners. In electrochemistry, a reversible capacity of 60 mAh/g (for 0.3K+) was delivers6.

In our presentation, we will detail the electrochemical behaviour of KFeO2 and discuss the structure/properties relationship of this family of materials, showing the interest in the exploration of such a system.

Xu, Y. et al. 2023 roadmap for potassium-ion batteries. J. Phys. Energy
5, 021502 (2023).

Tian, Y. et al. Promises and Challenges of Next-Generation “Beyond Li-ion” Batteries for Electric Vehicles and Grid Decarbonization. Chem. Rev.
121, 1623–1669 (2021).

Zhang, W., Liu, Y. & Guo, Z. Approaching high-performance potassium-ion batteries via advanced design strategies and engineering. Sci. Adv.
5, eaav7412 (2019).

Kim, H. et al. Investigation of Potassium Storage in Layered P3-Type K0.5MnO2 Cathode. Adv. Mater.
29, 1702480 (2017).

Liu, C., Luo, S., Huang, H., Zhai, Y. & Wang, Z. Layered potassium-deficient P2- and P3-type cathode materials KxMnO2 for K-ion batteries. Chem. Eng. J.
356, 53–59 (2019).

Han, S. C., Park, W. B., Sohn, K.-S. & Pyo, M. KFeO2 with corner-shared FeO4 frameworks as a new type of cathode material in potassium-ion batteries. J. Solid State Electrochem.
23, 3135–3143 (2019).
TiO2 Channel Material for Lithium-Ion-Gated Neuromorphic Transistors
Authors: Alvarez Ana , Schroeder Marshall A. , Boltersdorf Jonathan , Theodoru Stefan , Hoerauf John , Grew Kyle N.
Published: August 2024

Ubiquitous Internet of Things (IoT) platforms have exponentially increased the relay of an abundance of data between memory and processor in current computing architectures, ultimately limiting throughput and advancing towards the von Neumann bottleneck. Brain-inspired computing using neuromorphic devices presents an encouraging alternative framework capable of power-efficient real-time inference, self-learning, and decision-making. This work focuses specifically on ion-gated, three-terminal transistors that rely on electrochemically driven ion intercalation between an electronically insulating electrolyte and a conducting channel. While other nonvolatile memories (NVMs) can be used in neuromorphic devices, electrochemical random-access memory (ECRAM) advantageously enables the programming of multi-states and their retention in the absence of applied power. This talk will present our recent work on anatase TiO2 as a channel material in a lithium-ion-gated, three-terminal transistor. Based on the literature, anatase TiO2 covers a wide channel conductance range and exhibits a linear response, allowing for numerous well-defined synaptic weights [1]. We explore a range of channel conductance values using both potentiostatic and galvanostatic pulsing and correlate material properties to electrical measurements. These results provide a benchmark and roadmap for lithium-ion-based neuromorphic transistors capable of multi-states.

[1] Y. Li, E.J. Fuller, S. Asapu, S. Agarwal, T. Kurita, J.J. Yang, and A.A. Talin, ACS Appl. Mater. Interfaces
11, 38982 (2019).
(Invited) Bio-Inspired Time Varying Networks for Novel Computing Primitives
Authors: Kohlstedt Hermann
Published: August 2024

As a result of a hundred million years of evolution, living animals have adapted extremely well to their ecological niche. Such adaptation implies species-specific interactions with their immediate environment by processing sensory cues and responding with appropriate behavior. Understanding how living creatures perform pattern recognition and cognitive tasks is of particular importance for computing architectures: by studying these information pathways refined over eons of evolution, researchers may be able to streamline the process of developing more highly advanced, energy efficient autonomous systems.

With the advent of novel electronic and ionic components along with a deeper understanding of information pathways in living species, a plethora of opportunities to develop completely novel information processing avenues are within reach.

Basal biological principles are highlighted, including phylogenies, ontogenesis, and homeostasis, with particular emphasis on network topology and dynamics. While in machine learning, system training is performed on virgin networks without any a priori knowledge, the approach proposed here distinguishes itself unambiguously by employing growth mechanisms as a guideline to design novel computing architectures. Within this framework, experiments on low-frequency relaxation type oscillators coupled via complex time-varying networks will be presents. The spatio-temporal development of the network results from a mutual interaction between the oscillator ensemble and the network structure. The blooming and pruning of suddenly appearing conductive bridges and their relation to the synchrony state of the oscillator ensemble will be discussed.
Integrated Insights into NH4
+ Storage Mechanism and Electrochemical Kinetics of Ultrastable Prussian Blue Analogues
Authors: Zheng Runtian , Su Bao-Lian
Published: August 2024

Ammonium-ion batteries (AIBs) have recently attracted increasing attention in the field of aqueous batteries owing to their high safety and fast diffusion kinetics.[1, 2] The NH4
+ storage mechanism is quite different from that of spherical metal ions (e.g. Li+, Na+, K+, Mg2+, and Zn2+) because of the formation of hydrogen bonds between NH4
+ and host materials. As one of the main host materials, PBAs with 3D channels have been extensively investigated in AIBs. The formula for PBAs can be roughly expressed as AxMm[Mn(CN)6]y·zH2O, where A represents the cation (e.g. Na and K) for charge compensation, Mm and Mn stand for transition-metal ions (e.g. Cu, Ni), respectively. m, n, x, and y are their stoichiometric values. The size of the channels in PBAs is about 0.32 × 0.32 nm, which is larger than the ionic radius of NH4
+ (0.154 nm). In this work, the NH4
+ storage mechanism during the charging/discharging process is investigated by in-situ XRD and showed stable structure. In addition, the DFT calculation further demonstrates the insertion/extraction mechanism. During the NH4
+ insertion process, hydrogen bonds are formed between the hydrogen atom in NH4
+ and nitrogen atom in PBAs framework, which is beneficial for electrochemical and structural stability.

References

[1] H. Yu, L. Fan, H. Yan, C. Deng, L. Yan, J. Shu, Z.-B. Wang, Inorg. Chem. Front. 2022, 9, 2001-2010.

[2] X. Wu, Y. Qi, J.J. Hong, Z. Li, A.S. Hernandez, X. Ji, Angew. Chem. Int. Ed. 2017, 56, 13026-13030.
Electrochemical Hydrogen Storage Using Layered Double Hydroxide Material
Authors: Chauhan Himanshu , Yadav Ashish
Published: August 2024

In recent years, owing to the triple effect of increasing energy demand, depleting fossil fuels, and climate change, significant interest has been attracted in exploring hydrogen (H2) as an alternative or complementing clean and green energy sources. Various methods have been investigated for storing H2, however, electrochemical H2 storage has emerged as a viable method since H atoms are generated and stored in situ at normal pressure and temperature. The storage mechanism consists of, electrochemical reduction of H2O, thus leading to the generation of H atoms. These H atoms subsequently diffuse from the electrolyte, traversing through the adsorbed layer, and ultimately reach the electrode-electrolyte interface and get stored in the lamellar spaces of layered double hydroxide. The electrochemical H2 storage finds its application in Ni metal hydride batteries. Previously alloys were utilized as electrode material for electrochemical H2 storage however due to their complex structure, the storage process becomes sluggish. Moreover, the synthesis cost of alloys is very high since they employ techniques like arc welding. To address such limitations, the present research focuses on the fabrication of bimetallic layered double hydroxides-based H2 storage material. The synthesized material exhibited high discharge capacity, low resistance, and good cyclic stability. Thus, the proposed material synthesized through a facile route may be utilized as a viable potential alternative for efficient electrochemical H2 storage applications.

Figure 1
Enhancing Accuracy in Alkaline Water Electrolysis Studies: Insights from Hg/HgO Reference Electrode Potential Analysis
Authors: Kawashima Kenta , Marquez Raul A. , Son Yoon Jun , Guo Clarissa , Vaidyula Rinish Reddy , Smith Lettie A , Chukwuneke Chikaodili E. , Mullins Charles Buddie
Published: August 2024

This study addresses common misunderstandings surrounding using Hg/HgO reference electrodes in alkaline water electrolysis (AWE) research. Historically, numerous AWE investigations have relied on Hg/HgO reference electrodes, typically employing 1 M NaOH/KOH internal solutions, in three-electrode systems. Conventionally, the Hg/HgO (1 M NaOH/KOH) electrode potentials have been regarded as the half-cell standard reduction potential of the Hg/HgO electrode [0.0983 V vs SHE (standard hydrogen electrode) at 25 °C].1 However, it is crucial to note that the actual Hg/HgO (1 M NaOH/KOH) electrode potentials deviate from the half-cell standard reduction potential of the Hg/HgO electrode. To address this disparity, we present discussions and propose methodologies to calculate and experimentally determine real Hg/HgO electrode potentials.2 This approach enhances the precision of reporting AWE overpotentials and other performance parameters in various energy conversion devices operating in alkaline environments.

References

S. Niu, S. Li, Y. Du, X. Han, and P. Xu, ACS Energy Lett., 5, 1083–1087 (2020).

K. Kawashima et al., ACS Catal., 13, 1893–1898 (2023).
Bioinspired Multifunctional Nanocomposites for Energy Storage Applications
Authors: Emre Ahmet , Turali-Emre Emine , Kotov Nicholas
Published: August 2024

Bioinspired ion transport membranes have been extensively researched for energy storage applications. Sulfur, due to its natural abundance, low toxicity, high theoretical specific energy density (2600 Wh/kg), and high specific capacity (1675 mA/g), is attracting significant attention as an alternative battery system to replace traditional lithium-ion batteries that have limitations in terms of safety, capacity, and energy density in various applications. However, polysulfide dissolution and shuttling pose challenges that prevent the mass commercialization of metal sulfur batteries. We have developed a practical and comprehensive approach for developing high-performance metal sulfur batteries inspired by biological ion transport mechanisms. We used aramid nanofiber (ANF)-based composite ion transport membranes that prevent dendrite formation and confine polysulfides on the cathode side. ANF composite battery separators provide diverse and opposing properties, including high mechanical properties, high ionic conductivity, and high thermal/chemical stability. These biomimetic separators have highly selective ion-sieving properties that make the batteries safe and high-performing. It is crucial to fabricate such biocompatible, affordable, flexible, and high-energy-density batteries to power next-generation electronics such as portable, wearable, and implantable biomedical devices.
(Digital Presentation) In-Situ Growth of CNT and Macroporous ZIF on Bacterial Cellulose for High Frequency Electrochemical Capacitor
Authors: Baranwal Rishav Kumar , Lin Xueyan , Fan Zhaoyang
Published: August 2024

High frequency electrochemical capacitors (HF-ECs) represent a class of devices characterized by their high capacitive density and operational capability within the hundreds or kilohertz range. As electronic devices continue to undergo downsizing trends, HF-ECs emerge as promising alternatives to bulky aluminum electrolytic capacitors (AECs), which are constrained by their limited working frequency of approximately 1 Hz and slow charge-discharge rates. The designing of electrodes of HF-ECs combines large surface area for capacitive density along with open porous network to facilitate rapid ion transport. In this study, we synthesized nickel coordinated ZIF-8 (Zeolitic Imidazole Framework-8) cages on bacterial cellulose (BC). The samples underwent rapid carbonization in the presence of dicyandiamide at ~950˚C for 20 minutes, during which the zinc centers inside the MOF cages evaporated forming macroporous structures, while the nickel particles gave rise to carbon nanotube (CNT) growth through tip growth mechanism. The uniform coverage of BC with macroporous ZIF cages reduces the microporous effect, while the CNT growth also imparts higher electronic conductivity via graphitic nitrogen groups. The HF-ECs made with these electrodes and 6M KOH aqueous electrolyte gave a capacitive density of ~3.4 mFcm-2 and a phase angle of -81.3˚. The electrodes were stacked in pairs of 2 and 3 to achieve higher capacitance of 6.3 mFcm-2 and 8.9 mFcm-2 respectively. The HF-ECs were also assembled with 1 M TEABF4 in acetonitrile to show higher working voltage of these electrodes. The device maintained a capacitance just above 3 mFcm-2 and a phase angle over -80˚. The cells show an excellent working capability at higher discharge rates of 100 mAcm-2, where they retained ~70% of the initial capacitance.

Figure 1
Synergy of Silicon-Graphene Anodes and Polymer-Ceramic Hybrid Separators for High Rate-Capable Lithium-Ion Batteries
Authors: Joshi Yash Milind , Jain Ritika , Joo Yong Lak
Published: August 2024

With more and more electric vehicles (EV) hitting the market, the need for better and more robust energy storage system increases, and silicon has been a promising candidate for the next generation anode material to satisfy the high energy density and high-power requirements for electric vehicles because of its extremely high theoretical capacity. This has allowed the design of thinner electrodes to reduce the diffusion time scales and deliver a fast charge. However, at high charge and discharge rates, low electrical conductivity (~1.12 eV) of silicon hampers the battery performance. As a result, a lot of research has been conducted to improve the performance of silicon anodes using nanoscale carbon to increase the electrical conductivity. Graphene has been used to synthesize Si/Gr hybrid anodes due to its high conductivity.

Graphene nanoribbons (GNRs) , a part of the graphene family, are one-dimensional graphene nanostructures which tune its electrical properties based on dimensional confinement. GNR has a higher conductivity than Graphene. It also has high aspect ratio and surface area to provide a strong conductive path along with mechanical strength to support the silicon anode. Due to presence of GNR, lithium-ion transport into silicon nanostructures was enhanced. As a result, 50% of graphene was replaced by 50% GNR with silicon nanoparticles to form anodes. Due to the highly conducting structure of GNR, capacity at high rates was significantly improved because of the improved silicon utilization. Since GNR’s dimensions are in nanometer range, connection with silicon nanoparticles is better. It not only improves silicon to silicon conductivity, but it also acts as a filler for better connection of graphene with silicon nanoparticles.

Addition of graphene nanoribbons can improve the lithium-ion transport within the anode but to enhance the high charge transfer rate further, Si/GNR/Gr hybrid, high rate-capable anodes were paired with Polyimide (PI)/Polysilsesquioxane (PSSQ) hybrid separators which also shown to exhibit an improved charge transfer rate. At high rates such as 3C and 5C, the effect of separator on the cell performance becomes more prominent. While Celgard’s performance was very unstable at both 3C and 5C, at 3C, the cycling of hybrid separators did not get impacted, despite the relatively harsher conditions. This synergistic combination of high-rate capable silicon/graphene anode and hybrid separator outperformed the commercially used separator especially at high-rate cycling. Cells with Si/GNR/Gr anode paired with the PI/PSSQ separator delivered an impressive capacity of 1,000 mAh/g at high charge/discharge rates of 5C/5C.