bluuebunny/crossref_metadata_2025 huggingface dataset:
Understanding the Role of Liquid Electrolytes in Performance Improvement of Solid-State Lithium Metal Batteries
Authors: Yan Shuo , Merati Ali , Yim Chae-Ho , Baranova Elena , Weck Arnaud , Abu-Lebdeh Yaser
Published: July 2022

Abstract

Garnet-type Li7La3Zr2O12 (LLZO) Solid-State Electrolytes (SSEs) enable Solid-State Lithium Metal Batteries (SSLMBs) with high power density due to their superior ionic conductivity over 1 mS cm-1 at room temperature and good chemical stability against Lithium (Li) metal. A major cause of failure in SSLMBs is the large interfacial resistance between LLZO and electrodes. The high resistance at the interfaces is normally associated with insufficient solid-solid surface contact. It is a common practice to introduce a Liquid Electrolyte (LE) in SSLMBs either in combination with SSEs to form quasi-solid electrolytes or as the interface to enhance battery cycling performance. Several studies are conducted on resolving the contact issue between LLZO and the Li-metal anode but very few focused on the LLZO/cathode interface.

In this research, a carbonate-based LE was introduced at the interface of Li6.5La2.9Ba0.1Zr1.4Ta0.6O12 (LLBZTO) | LiNi0.6Mn0.6Co0.2O2 (NMC 622) cathode with the aim of understanding the mechanism which the LE enhances the SSLMBs performance, using the Scanning Transmission X-ray Microscopy (STXM) and X-ray Absorption Scanning (XAS). The assembled Li | LLBZTO SSEs | LE | NMC 622 cell exhibited an initial discharge capacity of 168 mAh g-1 with a capacity retention ratio of ~82 % after 30 cycles. The results from the STXM revealed the reactions of the LE with LLZO and NMC 622. The XAS analysis showed the formation of two new interfaces: Cathode-Electrolyte Interface (CEI) and Solid-Liquid Electrolyte Interface (SLEI). Also, the result indicated that the LE decomposed completely in the cell after 30 cycles and transformed to a dense and robust SLEI. This in turn led to the enhanced interfacial contact with the cathode and an improved Li+ ion transport at the interface. In addition, fluorides (i.e., LiF and LaF3) and carbonates (i.e., Li2CO3) were confirmed as the main components of the SLEI. In this study, two interfaces in SSLMBs (CEI and SLEI) were characterized. Fully understanding the roles of LE as the interface would enhance the practical application of quasi-solid electrolytes in SSLMBs.

Keywords

Solid-state lithium metal batteries; Garnet; Interface; Ceramic electrolyte; STXM
Investigation of Cathode Structure and Electrolyte Chemistry for Emerging Metal-Tellurium Batteries
Authors: Zhang Yue , Lu Wei , Freschi Donald J. , Liu Yulong , Liu Jian
Published: July 2022

Tellurium (Te) has received rising attention as electrode materials in next-generation high-energy-density rechargeable batteries due to its superior electronic conductivity and comparable specific volumetric capacity compared to conversion-type sulfur or selenium. To date, there is a lack of comprehensive understanding regarding the fundamental electrochemistry, structure design and electrolyte chemistry in emerging metal-Te battery systems. Herein, extensive efforts have been made in our group to figure out the role of carbon host in Te/C cathode architecture and construct highly stable Te/C cathodes. Our finding is that an ideal porous carbon is required to possess a majority of micropores to confine Te active materials and a small portion of mesopores to facilitate electrolyte wetting and Li-ion transport. Importantly, a durable Li-Te battery over 1,000 cycles at 2C was achieved with microporous carbon as Te host to constrain volume change of Te. A quasi-solid-state Li-Te is also constructed and demonstrates superior cycling and rate performance than Li-S/Se batteries with the same cell configuration. Moreover, the electrolyte chemistry and reaction mechanism in K-Te battery system are comprehensively revealed from the aspects of redox kinetics and surface chemistry. The two electrolyte salts (potassium hexafluorophosphate, KPF6 and potassium bis(fluorosulfonyl)imide, KFSI) induce similar phase transformation but different specific capacity, reaction kinetics, and SEI composition on the Te/C cathode. These findings are expected to promote the development of Te-based next-generation energy storage systems.
Plasma for Nano: A Green Approach for Next-Generation Energy Storage Applications
Authors: Santhosh Neelakandan Marath , Cvelbar Uros
Published: July 2022

Considering the increasing demand for advanced energy materials to meet consumer requirements, developing advanced high-performing materials at low cost in a green approach is the future step towards fabricating next-generation energy devices. The demand is not only for designing advanced materials but also for replacing rapidly exhausting lithium-based batteries. Therefore, different energy devices besides lithium batteries, such as potassium-ion batteries, multivalent metal-ion batteries, fuel cells, and electrochemical supercapacitors, have been investigated. Nevertheless, the performances of all these devices have to improve and update for obtaining the highest electrochemical performance for consumer applications. As the applied electrode materials highly influence the performance of energy storage devices, it is crucial to design high-performing electrode materials to improve the performance of energy storage devices. Even though several materials reported for high performance, the problems with capacity, rate capability, or electrochemical stability still have to be improved for high performance. Thus, research to produce all-in-one packaged electrodes at a low cost is gaining attention to address these issues. The most promising and widely accepted way to improve the electrochemical properties of electrode materials is their tailoring at the nanoscale. Plasma-enabled techniques can be used as a potentially clean and safe technique to tailor electrode structures at the nanoscale. Plasma assembles the nanostructures from gaseous into solid or solid to solid form on a substrate material. In addition, plasma catalysis properties can be used as a promising approach to designing hybrid structures with metal-anchored nanostructures. Moreover, plasma allows direct growth of material on the substrate, with the advantages of zero-waste production, cost-effectiveness and environmental-friendly nature. In this paper, the potential of plasma for designing hybrid nanostructures and the influence of plasma catalysis for the nanostructure synthesis with high structural quality and controllability is discussed to develop advanced electrodes at the nanoscale.
A Theoretical Investigation into pH of Neat Water at the Nanoscopic Scale Via Rexpon Force Field and Stochastic Simulations
Authors: Li Sirui , Kwon Soonho , Yu Ethan , Goddard William , Houle Frances
Published: July 2022

Design of durable solar CO2 conversion devices requires a mechanistic understanding of molecular-level reactions at the electrode-electrolyte interface that lead to interfacial degradation.[1] This interface often incorporates such features as a porous and rough surface to maximize active area and enhance catalytic performance. However, this roughness may introduce local water pool inclusions, whose size may have an unforeseen, detrimental impact on device durability due to their local pH being very different from the bulk pH. It is well-recognized that for water pools containing less than molecules, the solution pH cannot be defined in the conventional sense because the pools are too small to support stable water ion concentrations near neutral pH. Rather, the water ion concentrations fluctuate to very high values for short periods of time. To better understand pH in small pools, we combine theoretical calculations using QM/MD and stochastic simulations [3]. We combined Ab initio MD and the accurate RexPoN force field [2] simulation to quantify the thermodynamic free energy to create water ion pairs through the reaction as a function of the water pool size. The free energies are used to calculate the equilibrium constants for this reaction and the ion pair generation and recombination rate constants. The rate constants are then used as inputs to the stochastic simulations to gain insights into ion pair generation frequency and lifetime statistics over extended periods of time (hours). Proton and hydroxide diffusion are also incorporated in the stochastic simulation to understand how far water ions may travel from where they are generated. The results show that the combination of Grotthuss and vehicular diffusion mechanisms for H3O+ and OH- can lead to unequal distributions at an adjacent interface. We will discuss how the stochastic generation and recombination of water ions influences buffer chemistry and dissolved CO2 chemistry.

Reference

[1] S. Nitopi, E. Bertheussen, S.B. Scott, X. Liu, A.K. Engstfeld, S. Horch, B. Seger, I.E.L. Stephens, K. Chan, C. Hahn, J.K. Nørskov, T.F. Jaramillo, I. Chorkendorff, Progress and Perspectives of Electrochemical CO2 Reduction on Copper in Aqueous Electrolyte, Chem. Rev. 119 (2019) 7610–7672. https://doi.org/10.1021/acs.chemrev.8b00705.

[2] S. Naserifar, W.A. Goddard, The quantum mechanics-based polarizable force field for water simulations, J. Chem. Phys. 149 (2018). https://doi.org/10.1063/1.5042658.

[3] W.D. Hinsberg, F.A. Houle, Kinetiscope, (n.d.). http://www.hinsberg.net/kinetiscope.
Bipolar Electrochemistry for the Synthesis of Anodic TiO2 Nanotube Layers
Authors: Sopha Hanna , Macak Jan M.
Published: July 2022

Self-organized TiO2 nanotube (TNT) layers have attracted considerable scientific and technological interest over the past 17 years motivated for their wide range of applications including (photo-) catalysis, hydrogen generation and biomedical uses [1,2]. The synthesis of these TNT layers is carried out by electrochemical anodization of valve Ti metal substrates in various F--containing electrolytes using a conventional 2-electrode set-up with the Ti substrate as anode and a Pt-foil as cathode.

Instead of using a conventional set-up, also bipolar electrochemistry can be employed for the anodization of valve metals [3-7]. In this set-up, the Ti substrate is placed in an electrolyte between two so-called feeder electrodes, which are connected to the potentiostat. Due to the electric field between the feeder electrodes, the Ti substrate is polarized. If the applied potential between the feeder electrodes is high enough, redox reactions can be driven on the Ti substrate. This method opens new doors for the preparation of TNT layers with gradients in dimensions (i.e. diameter and length of the nanotubes) [3-5] as well as for the preparation of TNT layers on Ti substrates, which cannot be directly connected to the potentiostat, e.g. Ti spheres [8].

In this presentation, the preparation of TNT layers on small Ti spheres [8] as well as on 3D printed Ti substrates [9] using bipolar electrochemistry will be shown and discussed. Furthermore, we will also show the possibility of using closed bipolar electrochemical cells, consisting of two closed half-cells with the Ti substrate as obstacle between the cells [10].

References:

[1] J.M. Macak et al., Curr. Opin. Solid State Mater.
2007, 11, 3.

[2] Lee, K. et al., Chem. Rev.
2014, 114, 9385.

[3] G. Loget et al, J. Mater. Chem A
2014, 2, 17740.

[4] G. Loget et al., Langmuir
2014, 30, 15356.

[5] W. Wei et al., Electrochim. Acta
2015, 176, 1393.

[6] H. Asoh et al., RSC Adv.
2016, 6, 90318.

[7] H. Asoh et al., J. Electrochem. Soc.
2018, 165, C295.

[8] H. Sopha et al., Electrochem. Commun.
2020, 111, 106669.

[9] H. Sopha et al., Nano Lett.
2021, 21, 8701.

[10] H. Sopha et al., ChemElectroChem
2021, 8, 3827.
(Keynote) Zwitterionic Ferrocenes As Redox Flow Battery Components
Authors: Ziegler Christopher J.
Published: July 2022

Ferrocenes play increasingly important roles as cathodic components in redox flow battery designs. Peripheral functionalization has become an key tool in the development of ferrocenes as catholytes, as they can impart significant aqueous solubility. In this talk, two new aqueous soluble ferrocene compounds will be introduced that have zwitterionic functional groups pendant to the cyclopentadienyl ring. These compounds can be produced in one step from commercially available reagents and exhibit good stability and reversible electrochemistry in aqueous solution. We tested two such compounds in redox flow battery devices, and both exhibit superior performance characteristics. Notably, there is an observable difference in stability which corresponds to the length of the aliphatic chain between the cationic and anionic units, and we interrogated the factors behind this difference using computational methods.
The Role of Viscosity Variations: Analyzing and Modelling Microfluidic Membrane-Free Laminar Flow Batteries
Authors: de las Heras Miguel , Quintero Alberto Emanuel , Ibanez Santiago Enrique , Vera Marcos
Published: July 2022

Membraneless micro redox flow batteries prevent the advective mixing of catholyte and anolyte by operating at a small Reynolds number with flow rates of order 100µL/min or less [1] [2] [3] [4]. This laminar flow regime allows to remove the ion-exchange membrane used in conventional macro flow batteries. The absence of membrane decreases the internal electric resistance of the reactor, reduces manufacturing costs and potentially increases the performance of the system. However, removing the physical barrier between the electrolytes poses a new challenge: the accurate control of the thin region where both miscible electrolytes enter in contact. Undesired deflections of that mixing region (see Fig. 1) may lead to increased crossover losses and net liquid transfer between the tanks.

In this work we propose a numerical CFD model that sheds light on the behaviour of the mixing region at different flow conditions, considering viscosity changes in the electrolytes resulting from variations in the local state of charge during the operation of the cell. Then, a simplified dynamic model that includes electric current, flow rates and electrolyte properties as input parameters is proposed and validated against the CFD simulations. The present work constitutes the first study of membraneless micro redox flow batteries in non-ideal conditions arising from electrolyte heterogeneities. Our computationally efficient model allows to consider qualitative and long-term trends in a matter of minutes to hours, covering broad operation envelopes, which can be used to guide the design process of these emerging systems.

Figure 1: Undesired deflection of the mixing region

Acknowledgments

This work has been partially funded by the Agencia Estatal de Investigación (PID2019-106740RB-I00/AEI/10.13039/501100011033), and by Grant IND2019/AMB-17273 of the Comunidad de Madrid.

References

[1] Ferrigno et al. “Membraneless Vanadium Redox Fuel Cell Using Laminar Flow”. In: JACS Communications (2002).

[2] Choban et al. “Membraneless Fuel Cell Based on Laminar Flow”. Fuel Cell Science, Engineering and Technology. 2003.

[3] Kjeang et al. “A Microfluidic Fuel Cell with Flow-Through Porous Electrodes”. In: JACS Articles (2008).

[4] William Allan Braff. “Membraneless Hydrogen Bromine Laminar Flow Battery for Large-Scale Energy Storage”. PhD thesis. Massachusetts Institute of Technology, Feb. 2014

Figure 1
(Keynote) Bioelectrocatalytic Systems Based on Microcapsules, Glyconanoparticles and Microcavities
Authors: Cosnier Serge , Buzzetti Paulo Henrique , Nedellec Yannig , Brachi Monica , Gorgy Karine , Gondran Chantal , Shan Dan , Borsali Redouane
Published: July 2022

For four decades, the functionalization of electrodes by biomaterials based on electrogenerated polymers, carbon nanotubes and / or nano-objects, was widely used in the field of analytical chemistry and energy conversion. Recently, we redesigned enzymatic bioelectrodes in order to produce original objects. An innovative concept of reagentless biosensors based on enzymatic reduction of oxygen was developed by trapping and releasing the substrate of the enzyme (catechol) from the structure of the biosensor. A polyurethane support modified by two perforated microcapsules filled with catechol was easily transformed into a bioelectrode by the successive deposition of multiwalled carbon nanotubes and a mixture of laponite clay and tyrosinase enzyme [1].

On the other hand, the development of glyconanoparticles resulting from the self-assembly of block copolymers composed of polystyrene and cyclodextrin as an inclusion site will be reported. These glyconanoparticles, which are stable in suspension in aqueous media, have an outer layer composed of cyclodextrin [2]. The latter allows a post-functionalization of the nanoparticle by hydrophobic molecules through host-guest interactions. It appears that it is possible to modulate the site density of βCD at the surface of the shell of the hybrid glyconanoparticles while maintaining its inclusion properties. Moreover, the anchoring of glyconanoparticles to the surface of electrodes has been carried out by host-guest interactions with electrogenerated polymers. The efficient immobilization of the nanoparticles allows the anchoring of multilayers of biotinylated glucose oxidase.

Finally, a new generation of bioelectrodes for oxygen reduction and electrical energy production will be described. This approach is based on the design of flat electrodes made of permeable and conductive materials defining a very thin microcavity with a large surface area containing, in a microvolume, enzymes in powder form. The concept has been demonstrated with bilirubin oxidase (BOD) for the electroenzymatic reduction of oxygen in water. Besides the influence of the amount of enzyme trapped in the microcavity on the performance of the bioelectrode, the functionalization of the electrodes by adsorption of redox mediators or compounds allowing an orientation of the BOD favorable to electron transfer was also explored. After 5 months of storage in an aqueous buffer, the bioelectrode exhibits 20% of its initial electro-enzymatic activity.

Y. Nedellec, C. Gondran, K. Gorgy, S. MC Murtry, O. El Mazria, P. Agostini, S. Cosnier. Biosens. Bioelectron., 180, 113137-113141(2021).

M. Carrière, P. H. M. Buzzetti, K. Gorgy, M. Mumtaz, C. Travelet, R. Borsali, S. Cosnier. Nanomaterials 11 (2021) 1162. doi.org/10.3390/nano11051162.
The Behavior of Carbon-Coated Nanoparticles in Oxidizing and Reducing Gas Environment in Environment TEM (E-TEM) Mode
Authors: Doan Huong , Sgarbi Ricardo , Aouine Mimoun , Geantet Christophe , Chatenet Marian
Published: July 2022

The idea of a carbon-coated nanoparticles for electrochemical catalysis is not new and was widely used in direct methanol fuel cell (DMFC) [1], since the carbon coating acts as a barrier to prevent severe oxidation, thus protecting the nanoparticles from detrimental and irreversible degradation/corrosion. Recently, this type of catalyst was demonstrated to show excellent durability towards hydrogen oxidation and evolution reactions (HOR and HER), but also oxygen evolution and reduction reactions (OER and ORR), both in acid and (especially) in alkaline environment. For example, in alkaline media, Gao et. al and Doan et. al did show the excellent performance of carbon-coated Ni nanoparticles in both HOR and HER, vs. non-coated Ni; the latter degraded quickly because of severe oxidation/passivation or severe hydride poisoning. [2,3]

In this work, we synthesize carbon-coated Pd or Pd-Ni nanoparticles that are supported Vulcan carbon and study their electrochemical response in RDE. Their behavior is compared to non-carbon-coated Pd or Pd-Ni. The two kinds of catalysts materials are also thoroughly evaluated in environmental transmission electron microscopy (E-TEM) mode, using various temperature, either in high vacuum, oxygen, or hydrogen gas; these conditions were applied to mimic the inert or oxidizing/reducing environments witnessed in operating fuel cells and observe the behavior of the nanoparticles in such conditions. The experiments were conducted using a FEI TITAN E-TEM at IRCELYON, and the fast camera in the system provided the video of described experiments. It is shown that the carbon-coated Pd or Pd-Ni nanoparticles have enhanced robustness than their non-coated counterparts.

References

[1] Lo Vecchio, C.; Aricò, A.S.; Baglio, V. Materials
2018, 11(7), 1193.

[2] Gao, Y. et al. ACS Appl. Mater. Interfaces
2020, 12 (28), 31575–31581.

[3] Doan, H. et al.
J. Electrochem. Soc. 2021 168 084501
Atomic-Scale Investigation of the Reversible α- to ω-Phase Lithium Ion Charge – Discharge Characteristics of Electrodeposited Vanadium Pentoxide Nanobelts
Authors: Hussein Haytham E. M. , Beanland Richard , Sanchez Ana , Walker David , Walker Marc , Han Yisong , Macpherson Julie V.
Published: July 2022

Using an electrochemical potential pulse methodology in a mixed solvent system, electrochemical deposition of amorphous vanadium pentoxide (V2O5) nanobelts is possible. Crystallisation of the material is achieved using in air annealing with the temperature of crystallisation identified using in-situ heating transmission electron microscopy (TEM). The resulting α-phase V2O5 nanobelts have typical thicknesses of 10-20 nm, widths and lengths in the range 5-37 nm (mean 9 nm) and 15 - 221 nm (mean 134 nm), respectively. One-cycle reversibility studies for lithium intercalation (discharge) and de-intercalation (charge) reveal a maximum specific capacity associated with three lithium ions incorporated per unit cell, indicative of ω-Li3V2O5 formation. Aberration corrected scanning TEM confirm the formation of ω-Li3V2O5 across the entirety of a nanobelt during discharge and also the reversible formation of the α-V2O5 phase upon full charge. Preliminary second cycle studies reveal reformation of the ω-Li3V2O5, accompanied with a morphological change in the nanobelt dimensions. Achieving α-V2O5 to ω-Li3V2O5 to α-V2O5 reversibility is extremely challenging given the large structural rearrangements required. This phenomenon has only been seen before in a very limited number of studies, mostly employing nanosized V2O5 materials and never before with electrodeposited material.

Figure 1
(Invited) Measuring Molecular Weight of Poly(methyl methacrylate) through Electrochemistry
Authors: Kim Byung-Kwon
Published: July 2022

Rapid measurement of the molecular weight of a polymer is a crucial task both scientifically and industrially. Usually, the molecular weight of a polymer has been determined using the gel permeation chromatography (GPC), viscosity method (Ostwald, and Ubbelohde), nuclear magnetic resonance (NMR) spectroscopy, and other methods. However, they all share a critical weakness in that it is not possible to perform rapid measurement because of the long analysis times. To overcome this drawback, we propose a novel method for estimating polymer molecular weight using electrochemistry. In this study, poly(methyl methacrylate) formed by reversible addition-fragmentation chain transfer (RAFT) polymerization was considered as a model system. As polymerization progressed, a gradual decrease in steady-state current was observed in cyclic voltammetry. The decrease in current was compared to the molecular weights of the polymer obtained using the conventional methods of GPC and NMR. Therefore, the polymer molecular weight can be determined accurately and rapidly by measuring the current.
A Hand-Held Scanner for Dorsal Venous Network Pattern Identification
Authors: Shin YoungHo , Mohr Tristan , Kapany Rajbir , Leblanc Tyler , Taylor Joey , Conaway Nathan
Published: July 2022

For many years, medical professionals have relied on limited technology to locate the veins within their patients, however, this method has proven less effective for pediatric and elderly patients [1]. We propose a low-cost handheld scanner that determines the dorsal vein locations of a hand and uses the venous patterns to identify the patient. A hand dorsal vein pattern makes an excellent patient identification method in clinics or hospitals with more complex situations, as wearing personal protective equipment such as a mask can make it difficult to identify patients. The system also offers basic biological information about the patient, such as heart rate and blood oxygen saturation.

The scanner consists of 36 LEDs of red wavelength (625 nm) and NIR (near-infrared) wavelength (850 nm) which are used to display the dorsal vascular system. LED strips are incorporated into a 3D-printed jig that can be comfortably held by the patient. NIR LEDs are used as they are highly absorbed by oxygenated hemoglobin in the bloodstream, thus making veins more visible [2]. A webcam is used to capture the vascular pattern, which is then transferred and stored to the laptop computer for image processing and pattern recognition. The captured image is then processed through an algorithm consisting of multiple stages of filters to display dilated binary images of the vein patterns of the hand. As the light penetration rate of each patient's hand varies due to differences in skin color, thickness, and size, the scanner actively adjusts the intensity of the LEDs to increase the contrast of vein patterns. The images captured with different intensities of LED lights were subsequently analyzed using the algorithm developed to evaluate the ability to detect hand venous patterns.

In summary, we have developed a device and programmed an algorithm for processing an image of the dorsal venous network of the hand in real-time considering all possible hand characteristics. This device offers a new technological advancement for the medical field that could greatly benefit procedures used for vein finding in clinical settings in the future.

References

[1] V. M. Naik, S. S. P. Mantha, and B. K. Rayani, Indian Journal of Anaesthesia, 63, 737-745 (2019)

[2] A. Madrid García and P. R. Horche, Results in Physics, 11, 975-983 (2018)

Figure 1
Wash- and Separation-Free Electrochemical Detection of Proteases
Authors: Yang Haesik
Published: July 2022

Proteases play crucial roles in biological systems, including digestion, catabolism, and cell signaling. Indirect detection of Porphyromonas gingivalis in saliva, based on proteolytic cleavage by an Arg-specific gingipain (Arg-gingipain) protease, has traditionally been used for simple, initial diagnosis of periodontitis. To accurately detect P. gingivalis using a point-of-care format, development of a simple biosensor that can measure the exact concentration of P. gingivalis is required. However, electrochemical detection in saliva is challenging due to the presence of various interfering electroactive species in different concentrations. Here, we report a washing- and separation-free electrochemical biosensor for sensitive detection of P. gingivalis in saliva. Glycine–proline–arginine conjugated with 4-aminophenol (AP) was used as an electrochemical substrate for a trypsin-like Arg-gingipain, and glycylglycine was used to increase the Arg-gingipain activity. The electrochemical signal of AP was increased using electrochemical–chemical (EC) redox cycling involving an electrode, AP, and tris(2-carboxyethyl)phosphine, and the electrochemical charge signal was corrected using the initial charge obtained before a 15 min incubation period. The EC redox cycling combined with the matrix-corrected signal facilitated a high and reproducible signal without requiring washing and separation steps. The proteolytic cleavage of the electrochemical substrate was specific to P. gingivalis. The calculated detection limit for P. gingivalis in artificial saliva was 5 × 105 colony-forming units/mL, and the concentration of P. gingivalis in human saliva could be measured. The developed biosensor can be used as an initial diagnosis method to distinguish between healthy people and patients with periodontal diseases.

References

S. Park, K. Park, H. S. Na, J. Jung, H. Yang, Anal. Chem. 93, 5644 (2021)

S. Park, J. Shin, J. Kwon, W. Lee, J. Kim, G. Kim, J. M. Joo, H. Yang, ACS Sens. 6, 1305 (2021)

S. Park, G. Kim, J. Seo, H. Yang, Anal. Chem. 88, 11995 (2016)

S. Park, Y. M. Shin, J. Seo, J.-J. Song, H. Yang, Analyst 141, 2481 (2016)

S. Park, Y. Shin, J.-J. Song, H. Yang, Biosens. Bioelectron. 72, 211 (2015)

S. Park, H. Yang, Analyst, 139, 4051 (2014)
Insertional Profiling of Pyrroloquinoline Quinone Glucose Dehydrogenase for Two-Component Biosensor Engineering
Authors: Ngwadom Chiagoziem , Cai Rong , Ajo-Franklin Caroline
Published: July 2022

Colorectal cancer (CRC) is the third most common cancer worldwide and the second leading cause of cancer death. Currently, it is both expensive and invasive to screen for CRC. Developing a potential screening method that is more affordable and less invasive than endoscopy and biopsy would be beneficial to vulnerable communities. This method should also be able to diagnose and monitor the development and progression of GI cancers in real-time. A sensor that is capable of sending out an electrical signal in the presence of a cancer biomarker would alleviate the physical and economic costs of endoscopy while offering a significant amount of information about the gastrointestinal environment. Pyrroloquinoline quinone (PQQ) glucose dehydrogenase (PQQ-GDH), a redox enzyme, is capable of using glucose as a substrate for electron transfer. Engineering PQQ-GDH by insertion of a ligand-binding domain that is specific to a cancer biomarker would create an allosteric enzymatic switch that only produces current in the presence of the biomarker. To begin building this platform, I am creating a comprehensive insertion library to identify functionally important residues and domains of the PQQ-GDH. From there, I will profile which locations are capable of small primary, secondary, and/or tertiary structure disruptions. After identifying these regions, I will then create two-component protein switches capable of detecting cancer biomarkers. Creating an oxidoreductase switch that controls current transfer in the presence of gastrointestinal cancer biomarkers will advance the development of a novel, portable bio-recognition device capable of real-time, continuous sensing.
A Novel Electrochemical Differentiation between Exosomal-RNA of Breast Cancer MCF7 and MCF7/ADR-Resistant Cells
Authors: Abdelaziz Mohamed , Abd Elnaser Anwar , El Sawy Ehab
Published: July 2022

Improving health is a crucial social target that has a direct impact on better lives for billions and an indirect impact on the economy. Cancer is considered one of the most burdening diseases on better lives and hence the economy in all countries due to the high cost of health care and productivity deficiency. Therefore, the efforts to prevent, early detect, cost-effectively treat cancer become more important than ever. Chemotherapy is an essential step for cancer treatment in numerous cases. However, chemotherapy has severe side effects and a significant portion of patients do not respond to the treatment while suffering from these painful side effects. Doxorubicin, commercially known as Adriamycin, is a chemotherapy medication for several types of cancer. Our work aims for identifying the patients who have a resistance to Adriamycin chemotherapy.

Exosomes nanovesicles contain proteins, mRNA, and microRNAs (miRNAs) that exist in most body fluids and are expelled by multiple cell types including cancer cells1. Exosomes' unique composition allows them to represent their parental cells, which makes them promising biomarkers for tumor prognosis2. Conventional detection techniques necessitate enormous amounts of samples and extensive technical steps. Exosomal-RNA has been significantly used as a promising biomarker for tumor prognosis3. Herein, we describe the construction of a novel and cost-effective electrochemical system to sensitively differentiate between the exosomal-RNA of breast cancer MCF7 and MCF7/ADR-resistant cells, using four different electrochemical techniques; Cyclic Voltammetry (CV), Square Wave Voltammetry (SWV), Normal Pulse Voltammetry (NPV), and Differential Pulse Voltammetry (DPV). The high sensitivity of the proposed bio-electrochemical sensor opens the door for further investigation that address the other type of cancer cells.

References

R. Kalluri, Journal of Clinical Investigation, 126, 1208–1215 (2016).

H. Im, K. Lee, R. Weissleder, H. Lee, and C. M. Castro, Lab on a Chip, 17, 2892–2898 (2017).

D. Taller et al., Lab on a Chip, 15, 1656–1666 (2015).
Handling the Carbonates: Interfacial Engineering of Garnet Electrolytes
Authors: Cuevas Ignacio Andrés , Nkosi Funeka , Edstrom Kristina , Valvo Mario
Published: July 2022

Since Murugan et al. [1] discovered the Li7La3Zr2O12 (LLZO) inorganic solid state electrolyte composition, extensive work has been devoted to understanding its behavior and optimizing its structural and compositional features. Although improvement of its bulk and composition has allowed reaching ionic conductivities roughly in the range of mS/cm, much more work is needed in terms of assembling actual all-solid-state batteries by using this material.

In this work, we aim at a two fold improvement of the LLZO surface contact with the electrodes by not only creating a new layer on the surface of this ceramic electrolyte, but also by converting the non-conductive lithium carbonate layer [2] that forms on the LLZO surface upon air exposure. Through this rational approach, we expect a chemically relevant surface transformation, linked to a change in the electrochemical performance, via facilitation of the ionic transport through the surface of the ceramic pellet and an improved interface contact. LLZO pellets are treated with boric acid [3] in order to form borate species on their surface, substituting totally or partially the carbonate species that hinder ionic conductivity on the surface. The influence of both atmospheric

exposure, treatment and stirring on the resulting pellets is tracked via Raman, XPS and XRD analyses to obtain a comparison and assess the impact of these factors. The final effect of the boric acid treatment is checked via SEM-EDX and electrochemical impedance spectroscopy (EIS) analyses, to determine both morphological and electrochemical effects of the surface modification, which will further influence the interfacial characteristics of the pellet with both electrodes, with a special focus on the lithium side. Our results show an improvement of the surface properties of the pellets, due to the morphological and chemical modification of the LLZO surface, without

affecting the bulk properties.

[1] Ramaswamy Murugan, Venkataraman Thangadurai, and Werner Weppner. “Fast lithium ion conduction in garnet-type Li7La 3Zr2O12”. In: Angewandte Chemie - International Edition 46.41 (2007), pp. 7778–7781. issn: 14337851. doi: 10.1002/anie.200701144. [2] Asma Sharafi et al. “Impact of air exposure and surface chemistry on Li-Li7La3Zr2O12 interfacial resistance”. In: Journal of Materials Chemistry A 5.26 (2017), pp. 13475–13487. issn: 20507496. doi: 10.1039/c7ta03162a. [3] Yadong Ruan et al. “Acid induced conversion towards a robust and lithiophilic interface for Li-Li7La3Zr2O12 solid-state batteries”. In: Journal of Materials Chemistry A 7.24 (2019), pp. 14565–14574. issn: 20507496. doi: 10.1039/c9ta01911a.

Figure 1
Li(Ni,Co,Mn)O2 As Cathode Materials for Lithium Ion Batteries
Authors: Zhou Larissa , Luo Hongmei
Published: July 2022

Rechargeable lithium-ion batteries (LIBs) are widely used in cell phones, laptops, and electric vehicles. A LIB cell consists of three main parts: anode, cathode, and electrolyte. The battery type is named after its cathode materials, such as Li(Ni,Co,Mn)O2 (NCM) battery, which is composed of lithium, nickel, cobalt, and manganese. NCM has been the most used cathode for LIB industry due to its considerable capacity and energy density. NCM has different compositions, such as LiNi0.5Co0.2Mn0.3O2 (NCM 523), LiNi0.6Co0.2Mn0.2O2 (NCM 622), and LiNi0.8Co0.1Mn0.1O2 (NCM 811). With the applied NCM 622 and NCM 811 cathodes in coin cells in this research, the goal is to test their battery performance and to understand the composition effects on their electrochemical properties. From the charge-discharge and cycling performance measurements, NCM 811 shows higher capacity and better stability as compared to NCM 622. X-ray diffraction and electron microscopes are employed to examine the phase, morphology, crystal structure, and microstructure and to explore the relationship between composition, structure and battery performance. The goal is to have safe batteries with higher capacity, long cycling life and higher energy and power densities.
An Improved Pre-Lithiation of Graphite Anodes Using through-Holed Cathode and Anode Electrodes in a Laminated Lithium Ion Battery
Authors: Yamada Mitsuru , Gunji Takao , Tsuta Masaya , Nakamura Susumu , Soma Naohiko , Ando Nobuo , Matsumoto Futoshi
Published: July 2022

In order to actually compensate “an irreversible capacity (i.e., an active lithium loss) ˮ usually observed at the 1st charging/discharging cycle of lithium ion batteries (LIBs), e.g., caused by a solid-electrolyte interphase (SEI) formation, a so-called pre-lithiation was applied to the graphite anodes of the laminated cell composed of three graphite anodes and three LFP (lithium iron phosphate) cathodes which were through-holed with the hole diameter of 20, 100 or 200 μm like the squares of a “Go-board” (Fig. 1). The pre-lithiation was carried out (keeping an appropriate pre-lithiation charge amount) firstly by directly contacting the anodes with Li metal, which was previously introduced in the cell, to intercalate Li+ ions to them and then conducting the capacity balancing among the Li+-intercalated anodes by contacting them for a various period of time (Fig. 2). It was found that in the cell composed of the through-holed anodes and cathodes with a given hole diameter the irreversible capacity can be significantly reduced by appropriately choosing the pre-lithiation charge amount and the capacity balancing time. Typically, in the anodes (the hole diameter: 20 μm) with the total capacity of 35 mAh, when the pre-lithiation charge amount was 3 mAh and the capacity balancing time was 12 h, no irreversible capacity could be observed actually, i.e., the 1st charge capacity was close to 100% and the expected stable charge/discharge capacities were obtained with the capacity retention of almost 100% in the continuous charge/discharge cycle. The results obtained demonstrate that the pre-lithiation of LIBs can be significantly improved using through-holed anodes and cathodes.

Figure 1
Combining Promising Electrolyte Research and 3D Printing: Ionic Liquid Based Printable Membrane Materials
Authors: Lange Alyna , Zehbe Kerstin , Elamin Khalid , Abdurrokhman Iqbaal , Wojnarowska Zaneta , Paluch Marian , Taubert Andreas
Published: July 2022

As promising components in energy devices such as fuel or solar cells and batteries ionic liquids (ILs) are discussed due to their promising properties. These salts with melting points below 100 °C show e.g., high thermal and electrochemical stability, high ionic conductivities and non-flammability, making them interesting candidates for use as electrolytes.[1]

One of the most pressing global issues of our time, when disregarding the current COVID19 crisis, is the climate change with its well-known challenges concerning the climate policy and the energy economy. In this context due to their many benefits, the aforementioned fuel cells and batteries are being discussed as potential appliances, although there are some disadvantages attached to these technologies. Most polymer-electrolyte-membrane (PEM) fuel cells work with Nafion®, a sulfonated fluorocopolymer, as their membrane. Nafion® however loses conductivity at higher temperatures due to dehydration, limiting its operation temperature to around 80 °C at ambient pressure.[2] ILs are considered compounds that can overcome these limitations as they offer high conductivities even at elevated temperatures.

For the applications as electrolytes in the aforementioned systems the immobilization of the ILs is necessary, however, to prevent leaking and realize proper function.[1] The resulting ionogels (IGs) then combine the properties of the polymer matrix, i.e. its mechanical stability, with the characteristics of the respective IL. A suitable method to realize precise geometries and shapes for these membranes is given by 3D printing, which offers adaptable electrolyte design.[3]

The synthesis and characterization of ILs for ion (specifically proton) conduction is the aim of this work. These ILs exhibit wide electrochemical and thermal stability windows. The ionic conductivities of the investigated compounds range between 10-2 - 10-4 S/cm at elevated temperatures. The ILs are furthermore investigated under aspects of ion and proton transport via different spectroscopy methods.[3,4] Moreover, the ILs are immobilized in different matrix materials to provide flexible and transparent IGs that contain up to 80 wt% of IL. Additionally, successful 3D-printing and structuring of the IGs is also demonstrated.[3]

[1] M. Martinez, et al, Journal of Power Sources, 2010,
195, 5829-5839.

[2] J. Le Bideau, et al., Chem. Soc. Rev., 2011, 40, 907-925.

[3] K. Zehbe, et al., Energy Fuels, 2019, 33, 12885-12893.

[4] Z. Wojnarowska, et al., ACS Appl.
Mater. Interfaces,
2021, 13, 30614–30624.
Room Temperature, Ambient Pressure Synthesis of Urea By Electrolysis and Its Accurate and Consistent Measurement
Authors: Akther Jasmeen , Song Chaojie , Tsay Ken , Fatih Khalid , Pickup Peter
Published: July 2022

There is rapidly growing interest in the electrochemical reduction of both nitrite and carbon dioxide to mitigate environmental concerns and produce fuels and commodity chemicals (1). Urea is an important target in this area since it is the most widely used nitrogen fertilizer, and can also be used as a fuel and source of hydrogen. It can be produced simultaneously by electrochemical coreduction of NO2
- and CO2 (2-7). Various TiO2 based catalysts such as Cu-doped TiO2 (7) and FeTiO3 (4) have been reported to be effective for co-reduction of CO2 and NO2
-. Metallophthalocyanine catalysts have also been found to be effective in a gas-diffusion electrode configuration under ambient conditions (3).

The primary objective of this research is to develop fast and straightforward methodologies that can be routinely used to comprehensively evaluate and compare commercial and new catalysts for co-electrolysis of CO2 and NO2
- in an anion exchange membrane multi-cathode electrolysis cell under ambient conditions. The second objective is using this methodology to synthesize urea and develop reliable and consistent urea measurement methods using various techniques including spectrophotometric, 1H-NMR, mass spectrometry, and enzyme-based methods. It was found that NO2
- and the electrolyte can cause interference during urea measurement. In this research, commercial catalysts such as iron (II) phthalocyanine were used for co-electrolysis of CO2 and NO2
-.

Acknowledgements

This project is funded in part by the Government of Canada. / Ce projet est financé en partie par le gouvernement du Canada, and by Memorial University

References

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M. Shibata and N. Furuya, Electrochim. Acta, 48, 3953 (2003).

P. Siva, P. Prabu, M. Selvam, S. Karthik and V. Rajendran, Ionics, 23, 1871 (2017).

Y. G. Feng, H. Yang, Y. Zhang, X. Q. Huang, L. G. Li, T. Cheng and Q. Shao, Nano Lett., 20, 8282 (2020).

N. N. Meng, Y. M. Huang, Y. Liu, Y. F. Yu and B. Zhang, Cell Reports Physical Science, 2 (2021).

N. Cao, Y. L. Quan, A. X. Guan, C. Yang, Y. L. Ji, L. J. Zhang and G. F. Zheng, J. Colloid Interface Sci., 577, 109 (2020).
Optimizing Battery Manufacturing Decision-Making Using Lifecycle Assessment
Authors: Hsu Emily , Kleven Melissa
Published: July 2022

The global demand for batteries is projected to increase by 25% annually, reaching ~2,600 GWh in 2030. As the world shifts to electric mobility, particularly EVs, to reduce greenhouse gas emissions and mitigate the effects of climate change, research efforts on recycling and recovery of critical elements from lithium-ion batteries (LIB) have increased, leading to the development and advancement of technologies that utilize conventional and state-of-the-art recycling processes. Hydrometallurgical processing continues to be the most widely used method for recycling metals from LIB, but over the last few years, direct recycling has gained attention as a more sustainable and efficient process. While direct-recycling technologies are promising, most direct-recycling processes remain small in scale and are costly in terms of the equipment needed to recover metals from spent LIB. As such, materials selection in battery manufacturing and overall battery chemistry and design have become increasingly important. The development of new battery chemistries that are less reliant on critical metals, such as cobalt, has become a prominent area of interest, and material criticality has become a major driver for battery recycling and reuse.

Battery manufacturing is at a crossroads of decision-making with growing demands that overshadow available resources, reliance on imports, challenges in developing sustainable recycling processes that achieve increasingly stringent materials specifications, changing environmental regulations, and the need to identify and reduce potential environmental impacts for this growing waste stream. The best solutions will engage stakeholders from a variety of specialties who consider the battery lifecycle and the impact of each decision on the entire battery lifecycle. This presentation highlights one set of challenges - tradeoffs in materials selection with environmental regulatory compliance burdens and risks.
Electrons-Driven Recycling Processes As Alternative for Green Lithium-Ion Battery Recycling
Authors: Diaz Aldana Luis , Adhikari Birendra , Shi Meng , Klaehn John , Lister Tedd
Published: July 2022

Electrons sourced from low carbon energy sources can be used as a green reagent to enable hydrometallurgical recycling of lithium-ion batteries (LIB), significantly reducing the chemical consumption and carbon footprint of the recycling process. In this talk we will describe electrochemical driven alternatives for metals extraction and separation developed within the critical materials institute (CMI) for the recycling of end-of-life LIBs. The discussion will focus on how these technologies can be incorporated in the battery recycling flowsheet, and the impact of the electrochemical processes in the economic and carbon footprint of battery recycling