bluuebunny/crossref_metadata_2025 huggingface dataset:
A Paper-Based Surface-Enhanced Raman Scattering (SERS) Biosensor for Label-Free Detection of Serum Bilirubin for Diagnosis of Jaundice
Authors: Li Ming
Published: July 2021

Jaundice continues to be a serious health concern and is among the leading causes of deaths during the first days of newborn babies’ lives. Serum bilirubin is currently being exploited in the clinic as a key biomarker for the diagnosis and management of neonatal jaundice. The commonly used methods for serum bilirubin determination in clinical settings are direct spectroscopic measurement and the diazo reaction method. These methods have drawbacks such as low sensitivity, matrix interference, poor stability, high-cost, professional training, less specificity and tedious sample preparation. Thus, it is very urgent to develop a rapid and economical route for sensitive and specific detection of free bilirubin directly in human serum.

Surface-enhanced Raman scattering (SERS) has emerged as a powerful analytical technique for biosensing applications with high sensitivity, molecular specificity, powerful multiplex detection capability, and excellent photostability. This talk will present our recent study on the development of a paper-based SERS biosensor for label-free detection of bilirubin in serum. This biosensor comprises multifunctional graphene oxide-gold nanostar (GO-GNS) hybrids decorated on the filter paper. This biosensor combines the enrichment for serum bilirubin and plasmonic enhancement for Raman signals of bilirubin for boosting the label-free detection sensitivity directly in blood serum without the need for additional sample preparation. Our results demonstrated the excellent detection performance for detection of bilirubin directly in serum in a label-free manner, and the detection results were compared with the commercial diazo reaction method, which justifies the clinical effectiveness and suitability of the present paper-based SERS biosensor. We believe that the present paper-based SERS biosensor has great potential for clinical translation in accurate diagnosis of jaundice and other related diseases.

Reference:

Xiang Pan, Linhu Li, Hangduo Lin, Jiayi Tan, Haitao Wang, Mengling Liao, Caiju Chen, Beibei Shan, Yingfan Chen, Ming Li, A graphene oxide-gold nanostar hybrid based-paper biosensor for label-free SERS detection of serum bilirubin for diagnosis of jaundice, Biosensors and Bioelectronics, 2019, 145, 111713.
A 3D-Printed Microfluidic Device with Integrated Electrochemical Sensors for Autonomous Habitability Assessment and Life Detection
Authors: Thomson Seamus , Ricco Antonio , Koehne Jessica E. , Quinn Richard
Published: July 2021

A 3D-printed microfluidic device coupled with a fluidic processing system was developed to enable autonomous end-to-end sample handling and electrochemical characterization of an Ocean World analogue solution – synthetic seawater (SW). This dual-channel microfluidic cell was populated with 14 electrodes and performed electrochemical measurements similar to those used in the MECA Wet Chemistry Laboratory on board NASA’s Phoenix Lander that landed on Mars in 2008. Biological and metallic redox events were evaluated using cyclic voltammetry with Au, Pt, and glassy carbon electrodes, with the latter displaying superior sensitivity and selectivity. Conductivity and pH were measured using Pt and iridium oxide electrodes respectively, and SW anions such as chloride were quantified using chronopotentiometry with a Ag electrode. The fluidic handling system demonstrated sample transportation to the microfluidic device for electrochemical measurements, and could be readily adapted to accommodate different pre-processing steps. Overall, this study demonstrates the use of electrochemical sensors as part of an autonomous microfluidic handling system that would be functionally analogous to an electrochemical instrument designed for Ocean World exploration.
(Invited) Electrochemiluminescence Biosensing: From Bead-Based Immunoassays to Cell Microscopy
Authors: Sojic Neso
Published: July 2021

Electrogenerated chemiluminescence (ECL) is the process of light emission by the excited state of a luminophore upon electrochemical stimulation[1-2]. To increase the sensitivity and the multiplexing performances of ECL, many efforts have been focused on the development of novel analytical strategies and original imaging applications. In this lecture, we will present a few recent works on biosensing[3-5] and cell microscopy[6-7], which exploit the remarkable characteristics of ECL.

Bead-based ECL assays have been the object of numerous works and they are currently commercialized for more than 150 immunoassays. In a first part, new ECL approaches based either on the light polarisation or on semi-conductors will be presented to extend the performances of ECL[3-4]. In a second part, the development of coreactant-based ECL as a surface-confined microscopy to image single cells and their membrane proteins will be discussed[5-7].

References

A. J. Bard. Electrogenerated Chemiluminescence. M. Dekker. 2004.

N. Sojic. Analytical Electrogenerated Chemiluminescence: from Fundamentals to Bioassays. Royal Society of Chemistry. 2019.

F. Zinna, S. Voci, L. Arrico, E. Brun, A. Homberg, L. Bouffier, T. Funaioli, J. Lacour, N. Sojic, L. Di Bari. Angew. Chem. Int. Ed., 58, 6952 (2019).

Y. Zhao, J. Yu, G. Xu, N. Sojic, G. Loget. J. Am. Chem. Soc., 141, 13013 (2019).

M. Sentic, M. Milutinovic, F. Kanoufi, D. Manojlovic, S. Arbault, N. Sojic Chem. Sci., 5, 2568 (2014)

G. Valenti, S. Scarabino, B. Goudeau, A. Lesch, M. Jović, E. Villani, M. Sentic, S. Rapino, S. Arbault, F. Paolucci, N. Sojic. J. Am.
Chem. Soc., 139, 16830 (2017).

S. Voci, B. Goudeau, G. Valenti, A. Lesch, M. Jović, S. Rapino, F. Paolucci, S. Arbault, N. Sojic. J. Am.
Chem. Soc., 140, 14753 (2018).
MIP-Based Dye Displacement Assay for the Colorimetric Detection of Illicit Substances
Authors: Lowdon Joseph William , Rogosic Renato , Diliën Hanne , Eersels Kasper , van Grinsven Bart
Published: July 2021

Introduction:

In this study a novel molecularly imprinted polymer (MIP) based dye displacement assay is introduced for the rapid detection of the new psychoactive substance (NPS) sub-class known as diarylethylamines. The competitive nature of the assay facilitates displacement of a pre-bound dye molecule by a selected target molecule in a process coined Substrate displacement colorimetry (SDC).

Methods:

The assay was fully characterized by conducting affinity studies on the synthesized MIP, evaluating multiple dyes and expressing these affinities as binding factors (BF). The result of this study indicates the mathematical relationship between the established BF and the imprinting factor (IF) of the MIP towards the target analyte (2-MXP), allowing a prediction of efficacy towards dye displacement. Off the back of this study, dye-loaded MIPs were incubated with two common adulterants, two legal pharmacological, and the target diarylethylamine assessing the selective nature of the assay.

Results:

Of the dye’s tested malachite green was found to displace most readily when incubated with the target analyte, demonstrating easily quantifiable concentrations even when exposed to lower concentration of analyte. When incubated with the fore mentioned adulterants and pharmacological molecules, no dye displacement was observed; yet the target analyte stimulated clear dye displacement coloring the filtrate from the assay. This dye displacement was shown to be quantifiable, with a dose response being generated and the linear range of the assay determined by means of UV-visible spectroscopy.

Discussion:

The low–cost, robust and rapid nature of the proposed assay, combined with its tailorable selectivity and generic nature makes this an ideal tool for the screening of unknown seized samples. Displaying high sensitivity towards the desired analyte without sacrificing selectivity to other molecules, generating a highly reliable analytical protocol that can be both qualitative and quantitative depending upon the environment it is employed (Figure 1).

Figure 1
Investigation of Calcium Alloying with Sb, Sn and Bi As Negative Electrode Materials for Rechargeable Calcium Battery in Non-Aqueous Electrolytes
Authors: Baltruschat Helmut , Xing Da
Published: July 2021

Alloys were suggested as alternative anode materials for Ca metal anode because they have a high specific capacity and low overpotential. [1] A DFT study of CaxM has suggested a variety of alloy-type anode materials and considered the alloying voltage, volume expansion, and specific capacity. The metals such as Si, Sb, Bi, Al, Pt, Pb, and so on were predicted to be promising inexpensive anode candidates. [1] An Sn Nano-particular with a thickness of 25 μm was investigated for both the anode and current collector using 0.8 M Ca(PF6)2 in EC:PC:DMC:EMC (2:2:3:3) electrolytes. [2] It’s showed a high and wide voltage window (up to 4.8 V) and the cell could be cycled more than 300 cycles. The alloying compounds were found to be different phases with finally Ca7Sn6.

In this work, we study the fundamentals of the alloying process alloying of Ca thin film of bulk Sb, Sn, and Bi on polycrystalline Au using non-aqueous electrolyte (1.5 M Ca(BH4)2 in THF) at room temperature. Calcium stripping and plating using a Ca(BH4)2 in THF electrolyte shows high Coulombic efficiency (95 %) at room temperature on an Au substrate. [3] The cycling reversibility of alloying/de-alloying with Sb, Sn, and Bi have been demonstrated. The cyclic voltammogram for Ca insertion/de-insertion into Sb, Sn, and Bi-modified electrode shows a positive shift of the onset potential of Ca deposition compared to that at bare Au electrode. The ratio of moles of Ca to Sb, Sn, and Bi agrees with the stoichiometry of CaSb2, CaSn2, and CaBi3 alloy. Potential step were used to study the kinetics of insertion. The diffusion coefficient of Ca into the Sb, Sn, and Bi layers is calculated to be 10−14 𝑡𝑜 10−15 cm2s-1.

Acknowledgments: The authors acknowledge funding by the Federal Ministry of Education and Research of Germany (BMBF, FKZ; 03EK3027A).

[1] Z. Yao, V. I. Hegde, A. Aspuru-Guzik, and C. Wolverton, Advanced Energy Materials 9:1802994 (2019).

[2] N. Z. Wu, W. J. Yao, X. H. Song, G. Zhang, B. J. Chen, J. H. Yang, and Y. B. Tang, Advanced Energy Materials 9:7 (2019).

[3] D. Wang, X. Gao, Y. Chen, L. Jin, C. Kuss, and P. G. Bruce, Nature Materials 17:16 (2017).
Synthesis and Application of Metal Oxide/Graphene Oxide Nanocomposite Probe for Biosensing Methionine in Uremic Blood and Urine Samples
Authors: Eduok Ubong
Published: July 2021

Methionine (Met, Figure 1) is an essential amino acid in higher mammals as well as a substrate for most amino acids like taurine and cysteine. Met is responsible for cellular growth and development in humans since it contributes to the synthesis of most proteins as well as detoxify and regulate cellular aging. Changes in blood level Met may not be detrimental to human health, however, its contribution to regulating cysteine and homocysteine may contribute to some metabolic disorders in end-stage renal disease (ESRD) patients with no heart-related ailments. In the present study, a novel research approach toward synthesis of pencil probe composed of AgO/CuO/graphene oxide nanocomposites is presented. This probe was then utilized in biosensing Met in uremic blood and urine samples at the nano-level of detection. Prior to Met sensing, the synthesized probe was characterized using X-ray Photoelectron Spectroscopy, Raman spectroscopy and scanning electron microscopy techniques. Accompanying electrode reactions were monitored by means of cyclic voltammetry and electrochemical impedance spectroscopic techniques. The Ag-induced catalytic activity between pH 6-10 was observed following Met oxidation at the surface of the probe in the presence of hydroxide ions. Detection of Met was ascribed to the unique electroactive Ag and Cu sites of the probe. Its efficiency toward Met biosensing within both uremic blood and urine samples in the presence of potential sample-bound interferences was also investigated. With the emergence of complications involving some cardiovascular diseases associated with residual methionine in very few ESRD patients undergoing dialysis, this work presents a molecular nanao-level Met sensing as a disease biomarker. The lowest limit of detection for Met in this study was 45, 50 and 60 nM in the serum, plasma and urine, respectively.

Keywords: Biosensing; Disease biomarker; Methionine; Uremic blood; Pencil sensing probe

Figure 1. Molecular structure of methionine (Met) analyte.

Figure 1
Host-Guest Complex for Heparin Binding and Sensing
Authors: Välimäki Salla , Beyeh Ngong Kodiah , Linko Veikko , Ras Robin , Kostiainen Mauri
Published: July 2021

Heparin is a naturally occurring highly charged polyanion and a well-known anticoagulant widely used in surgical practice.[1] More specifically, it is a negatively charged sulfated polysaccharide belonging to the group of glycosaminoglycans. The anticoagulant effect of heparin is based on its ability to activate antithrombin-III, which, subsequently, inactivates vital coagulation cascade substance such as thrombin and factor Xa consequently preventing fibrin and clot formation.[2] To balance and neutralize heparin dosing, a heparin inhibitor is needed, and commonly, arginine-rich protein protamine sulfate (PS) is used for this purpose.[3] However, in recent years there has been an interest to investigate alternatives for protamine due to its adverse effects like hypotension and serious allergic reactions.[4]

In this study, a host-guest complex capable of selective heparin binding and sensing is presented.[5] Heparin binding affinity was studied in solution with a variety of polycationic macrocyclic hosts, a pillar[5]arene and multiple resorcin[4]arenes, by dynamic light scattering, dye displacement assay, isothermal titration calorimetry, and anti-Xa assay. The measurements reveal the significant importance of multivalency in the electrostatic host-heparin binding in competitive, application-relevant media. Additionally, to monitor heparin concentration, a host-guest indicator displacement assay was performed by following the free and bound state of methyl orange dye in UV-Vis spectroscopic experiments. Furthermore, this colorimetric sensing based on the tertiary host-guest-heparin supramolecular assembly was utilized in the construction of a calibration curve in a range of blood plasma concentrations.

Figure 1
Towards Tailored Carbon Nanotube-Based Fluorescent Sensors
Authors: Nißler Robert , Kruss Sebastian
Published: July 2021

Single-walled carbon nanotubes (SWCNTs) are an emerging building block for nanoscale sensors and labels because of their unique photophysical properties. Semiconducting SWCNTs fluoresce in the tissue transparency near infrared (nIR) window (840 – 1650 nm) and do not bleach. Due to their 1D nature small perturbations in their environment strongly affect their fluorescence. The major challenges in using SWCNTS for sensing is on the one side their purification and on the other side a tailored surface chemistry for molecular recognition and photophysical signal transduction.

Here, we present different approaches to tailor SWCNT surface chemistry and fluorescence emission properties for the detection of biologically important metabolites. Firstly, we tuned the sensitivity of ssDNA/SWCNTs against the neurotransmitter dopamine and different plant polyphenols by changing systematically the DNA sequence. In a more rational approach, we engineered DNA strands conjugated to small peptide sequences. In order to enable a ratio-specific linkage, we determined the amount of bound DNA on the SWCNT surface, which was further observed to play an important role in maintaining colloidal stability of the modified ssDNA/SWCNT conjugates. Finally, aptamer-based approaches were used to combine stable surface modification with target selective binding. For all these approaches we demonstrated via nIR-fluorescence spectroscopy and nIR-fluorescence stand-off imaging that tailoring these nanosensors resulted in an increased specificity against their targets, ranging from small chemical communication compounds (dopamine, H2O2) to cell wall components and secreted enzymes and metabolites. Lastly, we demonstrate that these tailored SWCNT sensors can also be transferred to purified nanotube building blocks, which enables a predictable design concept for sensor properties (emission wavelength and target specificity).
Platinum–Nickel Bimetallic Nanosphere–Ionic Liquid Interface for Electrochemical Oxygen and Hydrogen Sensing
Authors: Liu Xiaojun , Chen Xiaoyu , Xu Yong , Zeng Xiangqun
Published: July 2021

By exploiting the benefits of bimetallic platinum–nickel (Pt–Ni) alloy nanosphere and an ionic liquid (IL) (i.e., 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (BmpyNTf2), an organic–inorganic hybrid interface of IL/Pt–Ni was designed and characterized for electrochemical sensing of oxygen and hydrogen gases for miniaturized electrochemical gas sensor development. The spherical Pt–Ni alloy nanoparticles (NPs) were synthesized through template-free, one-pot solvothermal method. The morphology, crystal structure, and chemical composition of Pt–Ni alloy NPs were thoroughly characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The obtained Pt–Ni alloy NPs were used to fabricate the planar sensor devices and tested for oxygen and hydrogen sensing. The oxygen-sensing performance of the resulting planar electrochemical sensor was investigated over a low concentration range of 500–5000 ppm of O2 at room temperature by using constant potential amperometry. The planar electrochemical sensor device exhibited a high sensitivity to O2 ((3.04 ± 0.18) × 10–5 mA cm–2 ppm–1) compared to commercial Pt/C-based sensor ((2.57 ± 0.22) × 10–5 mA cm–2 ppm–1). The planar electrochemical sensor device also showed good reproducibility and selectivity for oxygen detection during sensing tests. Moreover, the sensor device based on the obtained Pt–Ni alloy NPs was investigated for hydrogen detection with excellent analytical performance in hydrogen sensing. The outstanding gas sensing properties were attributed to unique interface properties and highly efficient catalytic reaction of gas species of oxygen and hydrogen at the interface of IL/Pt–Ni alloy NPs. This work demonstrated that the integration of Pt–Ni alloy NPs with ILs enabled beneficial electrode interface for O2 and H2 gases sensing with high sensitivity, rapid gas response, and superior reproducibility based on a novel planar electrochemical sensor platform.
Dependence of Solid-State Metal Battery Thermodynamics on Interfacial Mechanics
Authors: Carmona Eric A , Wang Michael , Sakamoto Jeff , Albertus Paul
Published: July 2021

Next generation batteries seek to utilize metal electrodes due to their increased gravimetric and volumetric energy density compared to intercalation electrodes. Single-ion conducting solid electrolytes are viewed as a promising candidate to aid in the adoption of metal electrodes as they are mechanically stiff, possess high ionic conductivity, and may improve safety relative to conventional liquid electrolytes. Solid-state batteries are often constructed with an external stack pressure, and plating and stripping of the metal electrode leads to variable stress states in the cell during operation. The mechanical state of a material affects its thermodynamic state and can thereby lead to variations in the current distribution in the cell. This talk will focus on the effect of interfacial mechanics on the thermodynamic state of metal electrodes and single-ion conducting electrolytes. Experimental results and mechanics models will be shown to demonstrate the relationship. Disagreements in the literature regarding the appropriate stress terms to use when assessing the effect of mechanics on interfacial thermodynamics will be discussed. The talk will address how our new results can help to guide the development of future electro-chemo-mechanical plating and stripping stability models.
Developing Polymer Electrolytes with Balanced Thermomechanical and Conductive Properties through Incorporation of High Aromatic Content
Authors: Baroncini Elyse
Published: July 2021

Thermomechanical and electrochemical properties of thiol-ene polymers with high aromatic content afforded by lignocellulosic biomass were evaluated to explore feasibility and advantages in polymer electrolyte applications. Polymer electrolytes have the potential to mitigate stability and safety concerns accompanying incumbent liquid electrolyte systems in lithium-ion batteries. The thermal properties associated with low glass transition temperature (T
g) polymers are thought to improve contact with electrodes and ionic flow through the membranes compared to other liquid electrolyte alternatives such as solid electrolytes. Additionally, the high aromatic content of the lignin macromolecule can impart mechanical and thermal stability, making it attractive for use in applications that require robust polymers.

Low molecular weight fractions of wheat straw/Sarkanda grass soda lignin were functionalized and prepared through thiol-ene polymerization into polymer electrolytes. In combination with previous work, it was determined that differing solubility, functionality, and aromatic content of lignin fractions vary the glass transition temperatures of the resulting polymers and the suitability for electrolyte applications. The wheat straw/Sarkanda grass soda lignin utilized in solid polymer electrolytes (SPEs) displayed room temperature conductivity values in the range of 5 – 7 x 10-5 S cm-1. The lignin-based SPEs exhibited excellent cationic transport with ion transference values up to 0.90. Voltage stability and compatibility with electrode materials were also explored. The promising conductivity and ion transference results reveal the potential for use of functionalized, low molecular weight wheat straw/Sarkanda grass soda lignin in SPE applications as a way to improve thermal stability, electrochemical performance, and incorporate an abundant, sustainable resource in a high performance application.
Mechanism and Performance of a CO2-Driven Li-O2 Battery Containing LiBr
Authors: Marques Mota Filipe , Byon Hye Ryung , Kim Dong Ha
Published: July 2021

The environmental friendly aprotic lithium–oxygen (Li–O2) battery with high theoretical energy density has received great attention in the past years. A necessary shift to a direct exploitation of atmospheric air to assure the practicality of these devices has, however, demonstrated that the presence of CO2 and moisture fundamentally alters the O2 electrochemistry of the cell. The uncovered effect of CO2 in Li–O2 cells in a tetraglyme-electrolyte under a wide O2:CO2 mixture range revealed that with up to 30% CO2, the latter acts as an O2
− scavenger during discharge steps, leading to the formation of representative CO4
−/C2O6
2−-based species correlated with enhanced full capacity and cell cyclability. The CO2-driven Li–O2 device suffers, however, from unpractical recharge potentials at ~4.5 V required for the decomposition of Li2CO3. In this work, we investigate the performance of these devices in cells containing LiBr acting as a redox mediator. The electrochemically-generated Br3
–/Br2 redox couple offers a promising pathway to facilitate the decomposition of Li2CO3. We show that hindered overcharges (~0.5 V) are not only a function of the introduced LiBr concentration, but also depend on the crystallinity and morphology of the insulating Li2CO3 discharge product. Coupled electrochemical and spectroscopic analyses shed light on the redox shuttling steps at progressive states-of-recharge, revealing the presence of Br2···Br3
− loosely-bound anionic complexes in the electrolyte. As opposed to discrete polar Br2 irreversibly precipitated on the carbon-based cathode surface, the facile diffusion of the soluble Br2···Br3
− complex pinpoints these species as operating redox mediators. These findings offer insight toward the rational design of efficient mobile mediators beyond an overcharge decrease in the CO2-driven Li–O2 device.
Dual Pseudocapacitive Oxides Accelerate Kinetics of Sulfur Intermediates in Lithium-Sulfur Batteries
Authors: Liu Fang , Sun Geng , Dunn Bruce S. , Sautet Philippe , Lu Yunfeng
Published: July 2021

The sluggish electrochemical kinetics of sulfur species has impeded the wide adoption of lithium-sulfur battery, which is one of the most promising candidates for next-generation energy storage system. Here, we present the electronic and geometric structures of all possible sulfur species and construct an electronic energy diagram to unveil their reaction pathways in batteries, as well as the molecular origin of their sluggish kinetics. By decoupling the contradictory requirements of accelerating charging and discharging processes, we select two pseudocapacitive oxides to enable the efficient transport of electron/Li+ to and from sulfur intermediates respectively. After incorporating Li
x
Nb2O5/Nb2O5 as electron-ion source and MnO2/Li
y
MnO2 as electron-ion drain, the electrochemical kinetics of sulfur cathode is significantly accelerated by a factor of 5 times and 1.8 times, respectively. This strategy, which couples a fast-electrochemical reaction with a spontaneous chemical reaction to bypass a slow-electrochemical reaction pathway, offers a solution to accelerate an electrochemical reaction, providing new perspectives for the development of high-energy battery systems.
Evaluation of Redox Mediator’s Oxidation Stability in Lithium-Oxygen Batteries
Authors: Kim Hun , Kwak Won-Jin , Park Jiwon , Aurbach Doron , Byon Hye Ryung , Sun Yang-Kook
Published: July 2021

Employing organic redox mediators (ORMs) as mobile catalyst into the electrolyte system has been selected as an important strategy to lower the charging overpotentials in lithium-oxygen (Li-O2) batteries. Careful choice of molecular designs of ORMs can also tailor their redox potential and rate of electron-transfer to improve the catalytic efficiency. However, the stability of ORMs in Li–O2 cells was scarcely studied. In here, catalytic efficiency and stability of several important ORMs are assessed through in situ gas analysis and reactivity tests with singlet oxygen. Some well-known ORMs are detrimentally decomposed during the first cycle in Li–O2 cells, whereas nitroxyl-radical-based ORMs bear the most stable and efficient response. Analogous nitroxyl-radical derivatives further increase round-trip energy efficiency and electron-transfer kinetics. This study also emphasizes the evaluation of chemical stability of ORMs, which are mandatory for the long-term cyclability in Li–O2 cells.

references

W.-J. Kwak, H. Kim, H.-G. Jung, D. Aurbach, Y.-K. Sun, J. Electrochem. Soc.
2018, 165, A2274–A2293.

W.-J. Kwak, H. Kim, Y. K. Petit, C. Leypold, T. T. Nguyen, N. Mahne, P. Redfern, L. A. Curtiss, H.-G. Jung, S. M. Borisov, S. A. Freunberger and Y.-K. Sun, Nat. Commun., 2019, 10, 1380.
Tungsten Oxide/Zirconia As an Efficient Polysulﬁde Mediator for High-Performance Lithium−Sulfur Batteries
Authors: Bang Sangin , Kim Hun , Sun Yang-Kook
Published: July 2021

In this study, an eﬀective strategy is proposed to enhance the limitations associated with the use of a Li2S cathode in lithium−sulfur (Li−S) batteries. Tungsten oxide/zirconia (WO3/ZrO2) with a ratio of 3:7 is prepared and integrated into a 2D compacted Li2S−graphene matrix through pelletization. The newly developed composite material has a great potential as cathode material for Li−S batteries. In the composite cathode, presence of a metastable high-pressure Li2S phase enable the direct conversion of Li2S to S8 during the ﬁrst activation process, the high electrical conductivity of graphene, and simultaneously the integrated tungsten oxide/zirconia particles act as a polysulﬁde mediator to obstruct the outﬂow of soluble polysulﬁde into the electrolyte solution. Hence, the composite cathode shows high interfacial stability and thus substantially extends the lifetime of the Li−S battery over 200 cycles at a high Li2S loading of 10 mg cm−2. The practical Li−S full battery fabricated by combining the composite cathode and graphite anode provides outstanding cycle retention over 1500 cycles.

References

Hwang, J.-Y.; Shin, S.; Yoon, C. S.; Sun, Y.-K. ACS Energy Lett., 2019, 4, 2787−2795.

Lee, S.-K.; Lee, Y. J.; Sun, Y.-K. J. Power Sources, 2016, 323, 174−188.

Agostini, M.; Hassoun, J.; Liu, J.; Jeong, M.; Nara, H.; Momma, T.; Osaka, T.; Sun, Y.-K.; Scrosati, B. ACS Appl. Mater. Interfaces, 2014, 6, 10924−10928.
Non-Confinement Approach Towards Employing Carbonate-Based Electrolytes in Li-S Battery
Authors: Pai Rahul , Kalra Vibha
Published: July 2021

Rechargeable lithium-sulfur (Li-S) batteries have received increasing attention due to the high theoretical capacity of sulfur cathodes (1675 mAh.g-1), abundance, environmental friendliness, low toxicity and low cost of elemental sulfur. The commercialization of this technology, however, relies heavily on tackling yet unsolved operational issues that hinder the practical energy density delivered by Li-S batteries, such as (i) low electrical conductivity of sulfur and lithium sulfide (Li2S), (ii) severe capacity fade due to shuttling of long-chain lithium polysulfides, and (iii) lithium dendrite growth. In addition, another major obstacle towards commercialization is use of ether-based electrolytes owing towards its high flammability slightly above room temperature.

Carbonate-based electrolytes demonstrate safe and stable electrochemical performance in lithium ion batteries. Literature reports have demonstrated that sulfur can trigger substantial electrolyte decomposition due to formation of polysulfides to exhibit sudden battery failure. However, few types of cathodes with confinement of sulfur and cross-linking with polymer can be employed. However, higher sulfur loading, and improved conductivity of cathode still remains a prominent challenge in carbonate-based electrolyte. In this work, we have developed free-standing carbon nanofiber/S cathodes for achieving long-term cycling in Li-S batteries. The as-prepared CNF/S (1 – 5 mg.cm-2, ~50 wt% S) cathodes were used directly in 2032 type coin cells. The electrochemical tests were performed in EC:DEC based electrolyte against Li/Li+anode. The cyclic voltammetry and charge discharge results showed a single potential for conversion of sulfur to Li2S. The CNF/S cathodes delivered capacity of ~1300 mAh.g-1 during the first cycle with ~93% coulombic efficiency. The capacity of Li-S cells was stabilized at ~800 mAh.g-1 after Ist cycle and sustained up to 4000 cycles with only ~.01% decay rate per cycle. The postmortem XRD results confirmed the conversion of sulfur to Li2S and vice versa. Further, postmortem XPS analysis was conducted to understand the underlaying conversion mechanism. The preliminary results showed that the observed single plateau and long-term cycling of Li-S cells were the convoluted effect of deposited sulfur and digression from typical polysulfide formation route.
Cathode Electrolyte Interface Stabilization and Transition Metal Dissolution Mitigation Via Sodium Boron Salt Utilization
Authors: Kautz David J. , Mu Linqin , Lin Feng
Published: July 2021

Renewable energy storage devices have revolutionized the application of modern electronics and electrical infrastructures. The ever-increasing demand for large-scale energy storage has steered investigative interest to the rising potential of cost-efficient sodium ion batteries. However, the long-term cycling instability of cathode materials impedes wide-scale commercialization of sodium ion batteries. The interfacial reactions between the cathode and electrolyte has been shown to lead to prevalent surface reconstruction, transition metal dissolution, and the formation of intragranular nanocracks in the cathode particle, reducing overall cathode stability and cycling performance. Transitional metal dissolution can play a significant role in in performance degradation and further accelerating cathode particle instability. Investigating and improving the surface chemistry between the cathode and electrolyte is paramount to improving cathode stability and performance. We have designed a series of electrolytes that utilize select sodium boron salts that can passivate the O3-NaNi1/3Fe1/3Mn1/3O2 cathode and help form a robust cathode-electrolyte interphase (CEI). Through the utilization, and combination, of the sodium boron electrolytes, we observe improved cathode stability and long-term performance. We demonstrate enhanced cathode-electrolyte stability and cyclability at various temperatures ranging from 0°C - 45°C. Through improving the cathode surface passivation, we reduce interfacial reactions and observe a mitigation of transitional metal dissolution and migration from the cathode to separator or anode. Through this study, we demonstrate the importance of understanding the interfacial cathode-electrolyte surface chemistries and that there is further room for improving the electrolyte formulation for sodium layered oxide cathode materials.

L. Mu, X. Feng, R. Kou, Y. Zhang, H. Guo, C. Tian, C.J. Sun, X.W. Du, D. Nordllund, H.L. Xin, and F. Lin Adv. Energy Mater., 8, 1801975 (2018)

R. Jung, F. Linsenmann, R. Thomas, J. Wandt, S. Solchenbach, F. Maglia, C. Stinner, M. Tromp, H.A. Gasteiger, J. Electrochem. Soc., 166, A378–A389 (2019)

J. Chen, Z. Huang, C. Wang, S. Porter, B. Wang, W. Lie, H.K. Liu Chem. Commun., 51, 9809–9812 (2015).

The work was supported by the Virginia Tech Department of Chemistry Startup Funds, 4-VA Collaborative Research, and National Science Foundation (No. CBET-1912885). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-76SF00515. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory, under Contract No. DE-AC02- 06CH11357.
Understanding Sodium Ion Transport in Cathode Materials for Na-Ion Batteries Using MD Simulations
Authors: Seth Deepak , Haider M. Ali , Agarwal Manish , Anjum Uzma , Wani M. Shaharyar , Khan Tuhin S
Published: July 2021

Classical molecular dynamics (MD) simulations are applied to study the transport of Na-ions in cathode materials for Na-ion batteries (SIB). Two different materials (NaxV4O10 [1] and in NaxTi2(PO4)3) are studied to access and compare the level of Na-ion diffusion in electrode structure. Sodium constitute a potential alternative of Lithium in alkali metal batteries, since sources of Li are limited, and Na is readily available. The diffusion coefficient of Na-ions in SIB materials is reported in a wide range of experimental methods (potentiostatic titration, impedance measurements etc.). However, reported values differ from 2 to 4 orders of magnitude based on the experimental method used, since diffusivity estimates specifically from impedance curves are often measured away from the equilibrium and fitting parameters are prone to produce large errors. MD simulations using universal force field have provided a direct assessment of self-diffusion coefficient of Na-ions in the structure of NaxV4O10 with varying concentrations of Na-ions (0.33 < x < 1.33), calculating a diffusion coefficient of 5.75 x 10-8 cm2/s for x=0.66 at 300 K, which is in good agreement with experiments. Mean square displacement (MSD) and Na-ion density plots are further providing a mechanistic insight on the route of Na-ion transport.[2]

As a next generation material, NASICON structured type (NaTi2(PO4) SIB materials, are investigated for Na-ion transport. Inter-atomic based partial charge potential model is applied, and concentration of Na-ion is varied (from 0.82 <x < 0.98) in the supercell (total of 9000 atoms) of NaxTi2(PO4)3 at 323 K. Na+ transport of five different runs at varying concentration of Na+ are calculated and MD trajectory are visualized. MSD of Na+ as a function of time is shown as Figure. Self-diffusion coefficient of Na+ is calculated from the slope of MSD vs time plot for the three-dimensional transport, following Einstein’s relation. Calculated diffusivities are in the range of ~10-8-10-9 cm2/s and corresponding ionic conductivity is estimated to be (~10-4 S/cm). These values are in agreement with experimentally measured values of Na-ions in the similar structure.

References

Saroha, R., Khan, T.S., Chandra, M., Shukla, R., Panwar, A.K., Gupta, A., Haider, M.A., Basu, S. and Dhaka, R.S., 2019. Electrochemical properties of Na66V4O10 nanostructures as cathode material in rechargeable batteries for energy storage applications. ACS omega, 4(6), pp.9878-9888.

Wani, M.S., Anjum, U., Khan, T.S., Dhaka, R.S. and Haider, M.A., 2020. Understanding Na-Ion Transport in NaxV4O10 Electrode Material for Sodium-Ion Batteries. Journal of Electronic Materials, pp.1-6.

Figure 1
“Na Redistribution” Induced By K Intercalation during Na/K Ion Exchange in a Layered Oxide Cathode
Authors: Kim Haegyeom , Kwon Deok-Hwang , Kim Jae Chul , Ouyang Bin , Kim Hyunchul , Yang Julia , Ceder Gerbrand
Published: July 2021

An ion exchange reaction that can stabilize potassium transition metal oxides was proposed as a new approach to develop cathode materials for K-ion batteries (KIBs).1-4 Such ion exchange method indeed has frequently used for the development of novel Li-layered oxides to attain structural features of Na layered oxides.5-7 Although the ion exchange reaction has the potential to discover novel layered cathode materials by accessing the metastable states that cannot be achieved by conventional high-temperature solid-state reaction, the solid-state ion-exchange mechanism and the resulting phase evolution are barely understood.

In this study, we systematically investigate electrochemical Na+/K+ ion exchange in layered oxides. 8 Here, O3-type Na3Ni2SbO cathode is used as a model system.8 We found intriguing phase evolutions according to the relative Na/K content upon K intercalation by in-situ X-ray diffraction study. First, we observe that K-rich and Na-rich phases coexist during charging and discharging. Second, Na-rich phase goes through phase transformation upon K intercalation. Strong electrostatic repulsion between Na and K ions that have radically different bond lengths to coordinating oxygen ions can result in this complex phase evolutions. We uncovered that the intercalating K ions pushes away Na ions remaining in the desodiated Na
x
Ni2SbO6 phase, thereby separating Na-rich and K-rich phases in a particle. Interestingly, this phenomenon creates complex, three-phase equilibrium during the desodiation and potassiation processes in Na
x
K
y
Ni2SbO6: phase equilibrium between one K-rich and two Na-rich phases or two K-rich and one Na-rich phase is observed, as dictated by the Gibbs phase rule. Our computational study further demonstrated that this phase separation originates from the large lattice mismatch along the c-axis between the K-rich and Na-rich phases. Our observations and interpretations demonstrate that “ion-exchanged” systems may be more complex to interpret than the previously understood. Our analysis should be applicable to other ion-exchange systems where the exchanged ions are not well miscible in the host structure.

References

[1] S. Baskar et al. ECS Transactions
2017, 80, 357.

[2] N. Naveen et al. Chem. Mater.
2018, 30, 2049.

[3] J. Y. Hwang et al. Energy Environ. Sci.
2018, 11, 2821.

[4] H. Zhang et al. Chem. Commun.
2019, 55, 7910.

[5] C, Delmas et al. Mater. Res. Bull.
1982, 17, 117.

[6] A. R. Armstrong et al. Nature
1996, 381, 499.

[7] F. Capitaine et al. Solid State Ionc.
1996, 89, 197.

[8] H. Kim et al. Chem. Mater.
2020, 32, 4312.
A High-Voltage Potassium-Ion Battery with a Potassium Manganese Hexacyanoferrate Cathode
Authors: Wheeler Samuel , Fiore Michele , Hurlbutt Kevin , Capone Isaac , Fawdon Jack , Pasta Mauro
Published: July 2021

Potassium-ion batteries (KIBs) are a promising complementary technology to lithium-ion batteries that have the potential to be more sustainable and lower in cost. In KIBs lithium is replaced with potassium, the copper current collector is replaced with aluminium, and cathodes can be cobalt and nickel free. KIBs have the crucial advantage over sodium-ion batteries that potassium can reversibly intercalate into graphite whilst sodium cannot. Graphite offers a low operating voltage, high capacity, and good rate performance as a potassium-ion anode material.

There remain significant scientific challenges in the development of commercial potassium-ion batteries, notably developing high-capacity high-voltage cathode materials and electrolytes that are compatible with high-voltage cathodes and graphite anodes. In a recent perspective we identified potassium manganese hexacyanoferrate (KMF) as the most promising cathode material as it offers high energy density whilst also being low in cost [1]. However, the cyclability and coulombic efficiency of KMF are typically poor owing to parasitic reactions from water remaining in its structure and aluminium current collector corrosion among other mechanisms.

Here we present recent work to improve the performance of the KMF//graphite electrochemical system. Firstly, the citrate-assisted synthesis of KMF is optimised using high throughput synthesis and characterisation techniques to reduce the defect and water content whilst tailoring the particle size [2]. Secondly, an ionic-liquid based electrolyte, 1 M KFSI in Pyr1,3FSI (potassium bis(fluorosulfonyl)imide in N-butyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide)), is employed. This electrolyte successfully forms a passivating layer on the KMF cathode and surpresses aluminium corrosion which enables highly efficient cycling. Additionally, graphite operates exceptionally well with this same ionic-liquid based electrolyte.

We will end by offering our perspective on the current state of this research area and promising research directions.

References:

[1] Dhir, S.; Wheeler, S.; Capone, I.; Pasta, M. Chem
2020, 6 (10), 2442–2460.

[2] Fiore, M.; Wheeler, S.; Hurlbutt, K.; Capone, I.; Fawdon, J.; Ruffo, R.; Pasta, M. Chem. Mater.
2020, 32 (18), 7653–7661.
The Capacity Fading Mechanism of O3-Type Layered Oxide Cathode for Sodium-Ion Batteries
Authors: Yu Tae-Yeon , Sun Yang-Kook
Published: July 2021

A spherical O3-type layered oxide cathode, composed of compactly‐packed nanosized primary particles, is synthesized by the coprecipitation method so that the high tap density of the cathode ensures increased volumetric energy density for energy storage applications. However, drastic volume changes in the deeply charged states contribute to structural degradation, by inducing mechanical stress and the eventual disintegration of the cathode particles by the formation of microcrack. The microcrack traversing the entire secondary particle compromise the mechanical integrity of the cathode and accelerate electrolyte infiltration into the particle interior, causing the subsequent degradation of the exposed internal surfaces. In this study, we investigated the capacity fading mechanisms related to microcracks for the O3‐type Na[Ni0.5Mn0.5]O2 cathode which is one of the most widely studied materials for SIBs. The electrochemical performance cycled at different upper cut‐off voltages demonstrate that the P3′ to O3′ phase transition above 3.6 V is primarily responsible for the loss of the structural stability of the O3‐type Na[Ni0.5Mn0.5]O2 cathode.

References

S. Komaba, N. Yabuuchi, T. Nakayama, A. Ogata, T. Ishikawa, I. Nakai, Chem., 2012, 51, 6211.

H.-H Ryu, K.-J. Park, C. S. Yoon Y.-K. Sun, Chem. Mater. 2018, 30, 1155.
“Mirror-like” Electrodeposition of Lithium Metal Under a Low-Resistance Artificial Solid Electrolyte Interphase Layer
Authors: Hu Fei , Li Zhuo , Wang Shaofei , Tenhaeff Wyatt
Published: July 2021

Lithium metal is considered as the “holy grail” for next generation anode materials of energy storages. However, non-uniform electrodeposition of Li metal and dendritic growth result in low Coulombic efficiency and potential short circuits, leading to enormous capacity fading and safety issues. This is one of the key stumbling blocks to further development and commercialization of Li metal batteries. To suppress the dendritic deposition of Li metal, one strategy is to encapsulate the Li metal with an artificial solid electrolyte interface (ASEI) layer. The ideal artificial SEI layer should possess high mechanical strength and stiffness to prevent the intrusion of Li filaments, high Li transference number, low bulk/interfacial resistance, and high ionic yet negligible electronic conductivity. Moreover, recent studies show that the morphology of SEI layer is critical, and it is believed that a homogeneous, isotropic surface is required. The thin film solid electrolyte, lithium phosphorous oxynitride (LiPON), satisfies all of these properties. It has a relatively high shear modulus of 7.7 GPa, unity transference number, electrochemical stability window spanning from 0 up to 5.5 V vs. Li/Li+, ionic conductivity of ~2 × 10-6 S cm-1, electronic conductivity of ~8 × 10-13 S cm-1, and is fabricated as a smooth isotropic, homogenous thin film via physical vapor deposition. However, it remains a challenge to observe uniform, mirror-like electrodeposition of Li metal under the sole protection of LiPON layers.

Herein we propose a multifunctional ASEI that combines the advantages of LiPON coating protection with the enhanced electrolyte/electrode interface wetting conferred by LixAu alloys. “Mirror-like” electrodeposition of Li up to a practical capacity of 3 mAh cm-2 was achieved, guiding a new avenue towards the limited amount of Li electrode enabled by precisely controlled electrodeposition. The lithiation of Au films (as current collectors), significantly reduces nucleation overpotential to zero, promoting uniform electrodeposition of Li metal, thereby a more spatially uniform metal deposit. The low overall resistance ASEI layer (50 Ω cm2), LiPON, separates physically deposited Li and solvents from liquid electrolyte, drastically eliminating the electrolyte reduction and improving Li deposition efficiency. Operando impedance measurements were utilized to in-situ monitor interface differences during Li deposition.

Figure 1
Hybrid Solid Electrolyte Interphase for Dendrite-Free and Uniform Li Deposition
Authors: Pathak Rajesh , Baniya Abiral , Bobba Raja Sekhar , Qiao Quinn
Published: July 2021

Lithium (Li)-metal anode has attracted extensive attention owing to its high theoretical specific capacity (3860 mAh/g), which is more than ten times that of graphite anode (372 mAh/g). However, the notorious reactivity of Li-metal prevents their practical applications due to undesired Li dendrite growth and unstable solid electrolyte interphase (SEI) formation. Here, we developed a facile, cost-effective, and one-step approach for constructing an artificial Li-metal/electrolyte interface by treating Li metal anode with SnF2. As a result, the artificial SEI composed of LiF, Sn, and Sn-Li alloy was formed with higher ionic conductivity and increased Young’s modulus. The higher ionic conductivity and larger Young’s modulus of the artificial layer facilitate fast Li-ion diffusion and suppress Li dendrite growth, respectively. The hybrid artificial SEI showed a synergetic effect of storing Li by a reversible Sn-Li alloy formation and Li plating. The artificial hybrid SEI protected Li symmetrical cells showed outstanding plating/stripping cycles (~2325 hrs) with reduced overpotential compared to the bare Li. The high mass loading NMC cathode coupled with the SEI protected Li full cells exhibited remarkable electrochemical performance such as longer stable cycling, higher capacity retention, and higher capacity at higher rates compared to the bare Li anode.