bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) Nanosurface Fluidic Devices for Electrochemical Sensing and Biosensing
Authors: Mahshid Sara
Published: July 2021

Diagnostics of pathogenic and genetic disease (such as cancer) at the point of need, in particular at early-stage, requires dynamic manipulation and concentration of a small number of target molecules at individual single-molecule level, which currently limit microfluidic technologies. In my lab, we focus on engineering of new approaches in lab-on-chip technology via synergistically combining nanostructured materials with fluidic sample delivery systems to enhance the sensitivity and selectivity of the detection. Nanostructured materials boost the sensor resolution and show higher biochemical sensitivity and selectivity by significant amplification of the detection sites. We investigate 1) fabrication of novel nanostructured platforms based on 3D materials such as gold and 2D materials such as graphene and molybdenum disulfide, 2) integration of nanostructures with fluid sample delivery and biological assays (based on DNA/antibody) and 3) implementation of the device for detection of small molecules, pathogenic disease, and cancer genomics. In this regard, we address fundamental questions including: optimal interface of nanostructures with fluidic devices; target isolation, preparation and concentration in fluidic devices. We have successfully implemented the nanosurface fluidic devices for rapid and quantitative detection of bacteria such as Escherichia coli (E.coli) and Methicillin-resistant Staphylococcus aureus (MRSA), electrochemical detection of small molecules such as Dopamine and optical detection of extracellular vesicles (EVs).
Decorating Metal Oxide Nanostructures with Noble Metal NP for Bio-Sensing Applications
Authors: Almog Rakefet , Shashar Eden , Sverdlov Yelena , Shacham-Diamand Yosi
Published: July 2021

Biosensors based on functionalized metal oxide nanostructures, such as zinc oxide (ZnO) and Nickel Oxide (NiO), and have been demonstrated using electrochemical methods. Those nanostructures can be deposited on both rigid and flexible substrates at low temperature using rather simple and low-cost processes. Recently, it was discovered that decorating the metal oxide nanostructures with noble metal nanoparticles opens the doors to fabricating biosensors to detect volatile organic compounds.

The aim of this work is to improve the knowledge and understanding of a novel composite material structure where wide bandgap semiconductor metal oxide nanostructures are decorated with gold nanoparticles that their surface can be either decorated by functional biological material or converted to catalytic Pt (or Pd) shell. The metal nanoparticle surface functionalization poses some material-related questions regarding the behavior of that nano-structured material, especially when exposed to biological electrolytes or volatile organic compounds (e.g. Ethylene). This will allow us to develop a novel family of biosensors that enable sensitivity, rapidity, and selectivity for the detection of a wide range of target analytes, from pathogens to volatile organic gases, compared to existing bio-electrochemical sensors.

The final goal is a flexible all-in-one , highly sensitive and selective biosensors using relatively simple and low cost materials and processing. The sensors will use recent advances in functionalized Gold NP decorated ZnO and NiO electrodes based sensors.

ZnO nanowalls was deposited both on rigid (Silicon/ SiO2) substrate and on flexible (Polyimide) substrates. A Scanning Electron Microscopy study of the nucleation and growth of the ZnO nanowalls, and of the NP decoration was conducted. Different conditions such as growth temperature, concentration and time were used. RBS (Rutherford backscattering spectrometry) was performed on the ZnO nanowalls on Polyimide substrate.

After mastering the best methods for ZnO nanowalls growth and decoration with Au NP, decoration with different NP such as Platinum or Palladium will be compared. We believe that decoration of metal oxide nanostructures with noble metal nanoparticles will enhance the electrochemical performance of the sensors, for example - highly sensitive detection of VOCs such as ethylene.

This new structure should be further explored to reveal its full potential for flexible bio-sensor applications.

Figure 1
Enhanced Nitrogen Monoxide Gas-Sensing Performance of Ti-Doped ZnO Nanostructures By SILAR
Authors: Soltabayev Baktiyar , Yergaliuly Gani , Mentbayeva Almagul , Acar Selim
Published: July 2021

Fig. 1. Schematic illustration of SILAR fabrication process [1].

The use of semiconducting metal oxides to develop highly sensitive NO gas sensors remains an important approach in the field of gas sensing applications [2]. In this research, we describe the synthesis, characterization, and application of a very promissing NO gas sensing material ZnO doped with different atomic percentages of Ti and prepared by a simple SILAR [3] method. Synthesized specimens were structurally and morphologically characterized. The NO sensing characteristics of pristine ZnO and Ti-doped ZnO were compared using a gas sensing measurement system. The sensitivity, operating temperature, and response/recovery time were systematically investigated based on the change in electrical resistance of the materials in the presence of NO. Experimental results confirmed that 50 at% Ti-doped ZnO showed a maximum response to NO gas at an operating temperature. The sensing mechanism of the pristine and Ti-doped ZnO nanostructures is discussed in detail. We believe that the Ti-doped, flower-like ZnO nanostructure is a potential material for semiconductor-oxide-based NO gas sensors.

Key words: NO gas sensor, SILAR method, flower-like, Ti-doped ZnO.

Acknowledgement

This research was supported by the research grant 021220FD2201 “Development of highly sensitive MOS based nano-film gas sensors” from Nazarbayev University.

Reference

[1] B. Soltabayev, M.A. Yıldırım, A. Ateş, S. Acar, The effect of indium doping concentration on structural, morphological and gas sensing properties of IZO thin films deposited SILAR method, Mater. Sci. Semicond. Process. 101 (2019) 28–36. https://doi.org/10.1016/j.mssp.2019.05.026.

[2] V.S. Bhati, M. Hojamberdiev, M. Kumar, Enhanced sensing performance of ZnO nanostructures-based gas sensors: A review, Energy Reports. 6 (2020) 46–62. https://doi.org/10.1016/j.egyr.2019.08.070.

[3] T. Çorlu, I. Karaduman, M.A. Yildirim, A. Ateş, S. Acar, Effect of Doping Materials on the Low-Level NO Gas Sensing Properties of ZnO Thin Films, J. Electron. Mater. 46 (2017) 3995–4002. https://doi.org/10.1007/s11664-017-5503-z.

Figure 1
Direct Electrodeposition of Porous Graphene Films for Sensitive Detection of Bio-Compounds
Authors: Mohamed Nahla B.
Published: July 2021

Since its discovery, graphene continues to play a big role in the development of low-cost sensors thanks to its unique optical, mechanical, electronic and electrochemical properties. Here, we are going to present a simple approach for the direct electrodeposition of graphene foam from GO solution, providing an effective solution for the electrochemical sensing of redox-active species with high sensitivity. This is superior to previous approaches, in which graphene oxide is often applied to the electrode surface via drop-casting, alleviating its effective surface area and eventually compromising its output current. The present electrochemical method controls the electrostatic interaction between the negatively charged GO sheets and the surface of the electrode for the direct deposition of GO from solution under reducing potentials. This was made possible through the addition of cationic surfactant to GO deposition solution that is shown to improve the adsorption of GO sheets on the electrode surface, allowing for the effective reduction of its oxygen functional groups. This approach leads to the formation of a three-dimensional graphene framework with a very high effective surface area, which is successfully applied for the simultaneous analysis of dopamine (DA), ascorbic acid (AA), and uric acid (UA) with high sensitivity and selectivity. Abnormal levels of DA, AA and UA can lead to some critical diseases, such as Parkinson’s disease, hyperuricemia and leukemia. Therefore, it is considered of great important to develop reliable sensors for the simultaneous analysis of these compounds at physiological conditions. While traditional electrodes cannot distinguish these three biomolecules with an overlapping voltammetric oxidation peak, the new sensor shows three well-defined and completely resolved oxidation peaks along with a remarkable increasing electrooxidation current. Under optimal conditions of differential pulse voltammetry (DPV), the linear ranges for AA, DA, and UA are 2-3500 µM, 0.5-200 µM, and 5-250 µM, respectively. The corresponding detection limit (S/N=3) are 0.22, 0.11, 1.67 µM, respectively. The developed sensor demonstrates high sensitivity, good selectivity, well reproducibility and repeatability. Moreover, the proposed sensor was successfully applied for the simultaneous detection of AA, DA, and UA in real samples with good recovery. This method provides a new route for electrochemical reduction of graphene with a 3D network structure, which is a promising candidate for electrode material and other electrocatalytic applications.
Secondary Material Modified Anodic TiO2 Nanotube Layers As Efficient Gas Sensors
Authors: Sopha Hanna , Zazpe Raul , Ng Siow Woon , Macak Jan M.
Published: July 2021

Gas sensors are extensively used in medical, automotive, agriculture, biogas, and mining industry for safety and environmental monitoring, including the detection of toxic compounds to prevent hazardous emission and explosion as well as air quality monitoring. 1D nanomaterials have shown great potential for sensor preparation due to their high surface-to-volume ratios resulting in countless absorption sites, and fast diffusion of gas molecules. The 1D geometry also facilitates the charge transport process [1,2].

Among 1D nanomaterials, self-organized TiO2 nanotube layers have attracted considerable scientific and technological interest due to their wide possible range of applications including (photo-) catalysis, solar cells, hydrogen generation, biomedical uses or sensors [3,4]. The synthesis of the 1D TiO2 nanotube layers is usually carried out by electrochemical anodization of valve Ti metal sheets in various electrolytes. Compared to TiO2 nanotubes prepared by other methods (e.g. hydrothermal), anodic TiO2 nanotube layers have the advantage of being self-ordered with the nanotube openings on the top of the nanotube layer and being well-adhered to the Ti metal substrate, which can further be used as back contact for applications. Furthermore, anodic TiO2 nanotube layers can be produced with tunable tube dimensions [4]. Atomic Layer Deposition (ALD) can be used to produce conformal and homogenous coatings of thin layers of secondary materials an TiO2 nanotube layers, with precise control of the coating thickness, according to the deposition cycles [5]. Therefore, very thin films matching the thickness of the Debye length of a material can be deposited by ALD on the high surface area TiO2 nanotube layers giving the possibility for high sensitivity semiconductor gas sensors.

The presentation will focus on the coating of anodic TiO2 nanotube layers with secondary materials using ALD and the possible use for low concentration gas sensing. Such secondary materials are, for instance, SnO2 [6] and ZnO [7]. The produced heterostructures show excellent sensing behavior for NO2 [6], in case of SnO2 coated TiO2 nanotube layers, and for ethanol [7], in case of ZnO coated TiO2 nanotube layers.

References:

[1] S.-H. Jung et al., Sensors Actuators B Chem.,
2012, 171–172, 672.

[2] C. Marichy et al., Adv. Mater.,
2012, 24, 1017.

[3] J. M. Macak et al., Curr. Opin. Solid State Mater. Sci.,
2007, 1-2, 3.

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

[5] F. Dvorak et al., Appl. Mater. Today,
2019, 14, 1.

[6] S. Ng et al., ACS Appl. Mater. Interfaces,
2020, 12, 33386.

[7] S. Ng et al., Adv. Eng. Mater.,
2017, 1700589.
Ultrathin Ni(OH)2/Rgo Nanocomposite Chemically Deposited on Ni Foam for NOx Gas Sensors
Authors: Lokhande Prasad , Ghadge Vidhulatha , Gaikwad Nishant
Published: July 2021

Economical growth and increased population consume more natural resources also fossil fuel which leads to an increase in pollution. These pollutants directly affect human health as well as on the environment. Hence measurement of these pollutants has become an important research field nowadays. Present work demonstrates a hierarchical nanoflower-like Ni(OH)2/rGO nano-composite synthesized via a chemical deposition method on Ni foam as an electrode for NOx gas detection. The nano-flower like structure obtained comprised ultrathin nanosheets or nanopetals containing a porous nano-structure. Further, the addition of rGO enhanced the electrical conductivity of the synthesized material which is exhaustively exploited during the proton transfer process. The Ni(OH)2/rGO nanocomposite exhibited excellent NOx gas sensing properties such as high response time and high sensitivity.
Tourmaline Modified BiFeO3 Based MEMS Sensor with Temperature-Dependent Dual Selectivity for Detecting Acetone and Hydrogen Sulfide
Authors: Li Xiaojie , Xu Jiaqiang , Cheng Jinrong
Published: July 2021

In recent years, design and synthesis of heterostructured nanomaterials with high gas-sensing performance for detection of flammable and toxic gases has attracted much research interest. In this paper, pristine and tourmaline-modified BiFeO3(BFO) nanomaterials were successfully synthesized via a sol-gel method. The BiFeO3 modified with tourmaline could remarkably enhance the gas response and exhibit some novel properties. The tourmaline/BiFeO3 3wt% (tourmaline/BiFeO3 composite with the 3wt% tourmaline) MEMS sensor exhibited temperature-dependent dual selectivity to CO at 150 °C and H2S at 225 °C. The tourmaline/BiFeO3 3wt% based MEMS sensor response toward 0.77 ppm of acetone (C3H6O) is 4.3 at 150 °C and toward 0.75 ppm of hydrogen sulfide (H2S) reaches 11.6 at 225 °C. Furthermore, the sensor possessed good repeatability and antihumidity interference. The dramatically improved sensing performance could be ascribed to the spontaneous polarity of tourmaline, the electron transfer was modulated by the heterojunction in the interface between the BiFeO3 and tourmaline nanostructure. The easy fabrication and good gas sensing performances make our sensors highly attractive for ultrasensitive C3H6O and H2S gas detection with less power consumption.

Figure 1
Magnetic Graphene Based Cation Ion Exchange Material for Removal of Heavy Metal Ion (Pb2+) from Water
Authors: Kumari Poonam , Goel Disha , Mishra Sunita , Nayak Manoj Kumar
Published: July 2021

Abstract:

In current scenario, water pollution is a major worldwide problem. Many of the toxic heavy metals present in the water affected human body as well as aquatic animal life. Nowadays it has been a great attention to fast removal, cost-effective, sustainable detoxification/elimination of inorganic pollutants from wastewater. In this work, we have synthesized the magnetic Graphene-based hybrid nanocomposites, which is more sensitive and better supporting material for the removal of toxic pollutants from water. The hybrid nanomaterial was prepared by mixing iron (II) and iron (III) salt precursors in the presence of GO dispersion through the co- precipitation method followed by in situ chemical reduction of GO. Further, Magnetic Graphene Oxide (MGO) functionalized with the sulfonic acid group and oxidized by hydrogen peroxide (H2O2). The synthesis of magnetic graphene based nanocomposites was confirmed by X-ray diffraction (XRD), Fourier transformation infrared spectroscopy (FTIR), Raman spectroscopy, Field emission Scanning electron microscopy (FESEM) & EDS and magnetic behavior by vibrating sample magnetometer (VSM). Further, sulfonated magnetic graphene oxide (SMGO) (deposited on glassy carbon electrode) acts as a strong cationic exchanger, in which the negatively charged stationary phase electrostatically binds to the positively charged Pb(II) ions and Pb(II) ion exchange by hydrogen ion. The method exhibited a linear range of Pb(II), 1ppb-10ppm using CV. The CV, EIS and SWASV showed the incorporation of SMGO for electrode improvement with specific surface area, electrocatalytic activity and conductivity supported by GO sheets. This showed that enhanced analytical performance due to higher number of active sites, resulting higher ion exchange capacity and binding affinity of SMGO. It is a simple platform to develop novel electrochemical sensor for detecting heavy metals with high performance. Subsequently, regeneration of eco-friendly SMGO and corresponding reference method for quantitative detection and removal analysis of Pb(II) ions will be tested using ion chromatography method.

Figure 1
Design of Agricultural Autonomous Land Vehicles for Monitoring and Control
Authors: Vorobioff Juan , Boggio Norberto Gabriel , Checozzi Federico , Rinaldi Carlos
Published: July 2021

The world population is growing and it is necessary to take advantage of agricultural natural resources. According to FAO studies, undernourishment is increasing in almost all sub-regions of Africa, as well as in South America. The situation worsens in countries whose agricultural systems are extremely sensitive to rainfall, temperature and droughts. On the other hand, contamination by pesticides and herbicides generates a series of environmental problems. In addition, the insects and parasites themselves develop more resistant species, which forces the use of higher doses or more effective products. Due to the rains and flooding of the fields, the chemicals are transmitted to the rivers, contaminating the water, vegetation, livestock and people. There are unmanned aerial vehicles known as drones to monitor fields, but they are expensive and require qualified personnel. In this work, a low-cost and reduced-size autonomous land vehicle (car) is designed to monitor fields. An electronic nose is mounted with 7 low consumption metal oxide semiconductor (MOS) gas sensors and batteries. The size and scope of the vehicle can be changed by modifying the structure of the car using a 3D printer, changing batteries and motors. Solar panels can also be added for extended use. The electronic nose weighs only 50 grams, has small dimensions, is low cost, has an embedded system and proprietary software. The software stores the data in memory, using artificial intelligence, different odors can be recognized in a field. In this way, a map of the monitored terrain is assembled and it can be fumigated in a controlled manner, selecting different doses as necessary. This system is expected to reduce environmental pollution and improve agricultural production.

Key Words: Autonomous Vehicle, Agriculture, Electronic Nose, Data Analysis.

References

[1] J. Vorobioff, E. Videla, N. Boggio, O.D. Salomón, A. Lamagna, C.A. Rinaldi. Sensors and Actuators B: Chemical, 257 (2018), pág. 200-206, ISSN 0925-4005

[2] P. Neumann, S. Asadi, J. H. Schiller, A. J. Lilienthal, and M. Bartholmai, IEEE Robotics and Automation Magazine, 19 (2012), pág. 50-61.

Figure 1
Passive Surface Acoustic Wave Sensors for Early Corrosion Onset Detection
Authors: Devkota Jagannath , Greve David W. , Jee Youngseok , Lu Fei , Diemler Nathan , Wright Ruishu , Buric Michael
Published: July 2021

Corrosion creates serious safety concerns and economic burden in fuel processing and transportation. Being able to monitor the infrastructures in real time and detect corrosion onset may prevent potential consequences resulting from their failure. Passive wireless surface acoustic wave (SAW) devices are promising passive devices to detect the presence of water and corrosion onset amongst other parameters in natural gas pipelines and wellbore tubes. Here, we present on the possibility of using shear horizontal (SH-) SAW devices for monitoring metal film dissolution in hydrochloric acid of varied pH. 520 MHz SH-SAW reflective delay lines with two reflectors were fabricated on 36°Y-X LiTaO3, of which a channel was coated with 60 nm thick iron film by magnetron sputtering. With the film, the sensor had a center frequency of 529.8 MHz when measured in air. The sensor showed a slight attenuation and small frequency shift in DI water. In HCl solution with pH 2.01, the sensor’s center frequency first decreased with time for the first six minutes to reach down to 521 MHz and then remained almost unchanged. The S11 magnitude also showed similar behavior. After ten minutes immersion into the corrosive solution, no iron film was left under a visual inspection. The decrease in the frequency and attenuation is probably due to the changes in the mass and elasticity and the film surface roughening, respectively. Observed initial results are promising towards the implementation of SAW devices for monitoring corrosion in metallic structures in real time.
Osmotic-Capillary Principles for Microfluidic Pumping and Fluid Management for Sweat Sensing Devices
Authors: Saha Tamoghna , Fang Jennifer , Mukherjee Sneha , Daniele Michael A. , Dickey Michael D , Velev Orlin D.
Published: July 2021

Sweat is an essential biofluid for monitoring individuals’ health as it contains several key biomarkers. However, sampling sweat for analysis is still challenging as most of the commercially available sweat sensing devices are either invasive in nature or work only during active perspiration. These devices may not function under low-sweating conditions and may be incapable of sensing in sweat from sedentary subjects. We demonstrate a new principle for the design of flexible and wearable devices, which are capable of extracting sweat under both resting and actively perspiring conditions using osmotic pressure difference for pumping, and evaporation for liquid disposal (Biomicrofludics, 14, 034112, 2020). The device is composed of silicone, hosting polyacrylamide hydrogel patch, and paper microfluidic conduit with a site of evaporation at the end (evaporation pad). The hydrogel is equilibrated with glycerin, glucose, or NaCl solution to build up the desired osmotic strength to extract fluid from the skin. We investigate their operation using a model biomarker (dye) solution. In-vitro testing with gelatin-based model skin platform revealed that both glucose and glycerin-infused gels facilitate high analyte accumulation on the evaporation pad, with glucose as osmolyte having the highest driving pressure. The cumulative dye collection also depends on the dimensions of the paper channel, hydrogel area and paper porosity. Human trials show potential to extract sweat and analyze it for lactate under both resting and non-resting conditions within a period of two hours. This sweat sampling concept can be integrated in continuously operating wearable devices using enzymatic electrochemical sensors. We used lactate as a concept demonstrator, as sweat appears to be more informative medium for lactate quantification than blood. The ability to measure lactate enables monitoring metabolism and oxidative stress levels in athletes and military personnel.
Fe/SiO2 Composite Coated Optical Fiber for Corrosion Monitoring
Authors: Wright Ruishu , Diemler Nathan , Egbu James , Ohodnicki Paul R.
Published: July 2021

It is important to monitor and locate internal corrosion over the long-distance natural gas pipelines in real time before catastrophic failures to ensure safe, secure, and reliable transportation of natural gas and reduce the environmental impact from methane emission. Optical fiber based sensors provide many advantageous features, especially the distributed sensing over a long distance and the inertness in the presence of flammable gas, among others. To take advantage of these features, corrosion proxy sensing materials are a key enabling component for an optical fiber corrosion sensor. We have previously demonstrated a distributed optical fiber corrosion sensor, and reported early results on Fe/SiO2 composite coating. To further improve the sensing performance, detailed studies were performed to investigate the Fe/SiO2 composite coating. The Fe/SiO2 composite layers are coated onto the optical fiber using sol-gel and electroless plating methods, respectively, with controlled morphologies. The coating is characterized with SEM and XPS. Tested in corrosive solutions at room temperature, optical responses are measured for corrosion monitoring. The light transmission increases as Fe dissolves away due to the decrease in light absorption of the metallic layer. Different morphologies are compared to optimize sensing performance of the Fe/SiO2 composite coated optical fiber corrosion sensor.
Solid Electrolyte Interphase for Ca Metal Batteries
Authors: Bodin Charlotte , Forero-Saboya Juan , Davoisne Carine , Dedryvere Remi , Yousef Ibraheem , Ponrouch Alexandre
Published: July 2021

New battery technologies have received increased attention in recent years, especially those based on the use of divalent cations such as calcium and magnesium. Their high abundance (calcium and magnesium being, respectively, the 5th and 8th most abundant element in the earth crust) and the possible safe use of metal anodes could result in more sustainable devices with lower cost and higher energy density systems when compared to Li-ion. Feasibility of plating/stripping of calcium metal has been demonstrated recently1 in very few organic electrolyte formulations. In all cases, some degree of electrolyte reduction and formation of passivation layer were reported. In particular, using Ca(BF4)2 in a mixture of carbonate solvents, a fully conformal passivation layer is formed at the surface of the metal anode.2 Yet this layer allows for Ca plating and stripping, thus exhibiting similar behavior as a solid electrolyte interphase (SEI). However, the nature and composition of such layer remain mostly unknown.

In this communication, an in-depth analysis of the SEI will be presented. The influence of the electrolyte formulation (salt, solvent and additive) on the formation of the SEI and how it affects Ca plating and stripping kinetics were investigated. Among other technics, XPS, EELS and ToF-SIMS measurements allowed to detail the composition of the SEI. The homogeneity, the morphology and the microstructure were studied by means of TEM and FTIR microspectroscopy.

Ponrouch, A. et al. Towards a calcium-based rechargeable battery. Nat. Mater.
15, 169 (2015).

Forero-Saboya, J. et al. Understanding the nature of the passivation layer enabling reversible calcium plating. Energy Environ. Sci.
13, 3423–3431 (2020).
Complex Dynamics at the Aqueous Zinc-Ion Battery Cathode Interface
Authors: Becknell Nigel , Lopes Pietro , Tepavcevic Sanja , Stamenkovic Vojislav
Published: July 2021

Aqueous energy storage systems provide complex and unique challenges due to electrolyte and material instability in the realistic potential window of interest. The inherent intrigue of aqueous systems is the safe, low-cost, environmentally friendly nature of the electrolyte. In the interest of using low-cost, non-toxic materials, we studied the evolution of manganese oxide in aqueous zinc-ion batteries, highlighting and utilizing its instability. Aqueous zinc-ion batteries in near neutral electrolyte were initially developed as an analogy to the rocking chair Li-ion battery, targeting employment of a Zn-intercalation mechanism at the cathode. However, the nature of the aqueous system means that other effects such as Mn-dissolution, proton-intercalation, water electrolysis, and the effect of pH must be considered. A combination of materials and electrochemical characterization reveals the dominant challenge in this system to be the irreversible phase changes of manganese oxide and concurrent Mn-dissolution. We find that the electrolyte has a major influence on the trajectory of the cathode material. Ultimately, we transform the instability of the electrochemical interface from an obstacle into an advantage and reveal the potential for batteries to leverage a dynamic interface.
(Invited) Organic Semiconductor, Receptor Material and Circuit Design for Organic Electronic Vapor Sensors and Biosensors
Authors: Katz Howard E.
Published: July 2021

We will present our recent results on the design of semiconducting material, gate structures, and stabilizing and amplifying circuits for detection of volatile analytes in the atmosphere and proteins in aqueous solution. Besides our natural interest in designing materials that respond more strongly to analytes of interest than to likely interferents, we also emphasize the use of chemical and electronic amplification methods to increase the ratio of the desired responses to the drift (signal/noise ratio). Printable materials, especially polymers, are emphasized for the responsive layers. The use of multiple sensing elements, typically field-effect transistors (FETs), to create patterns of responses increases the selectivity of the information, either by narrowing the classes of compounds providing the responses, distinguishing time-dependent from dose-dependent responses, and/or increasing the ratio of analyte responses to environmental drifts. As a specific example, using pairs of FETs, in series or in parallel, allows device drifts to be substantially canceled while analyte responses are maintained and even reinforced. This strategy has led to significant improvements in the use of polymer-based FETs to detect pollutant gases such as nitrogen dioxide and ammonia. To increase the stability of systems used to detect analytes in solution, we sometimes separate the sensing surface from the output device in an arrangement known as a remote gate. We show that the output device may be an organic-based or a silicon-based transistor, and can respond to electrochemical potential changes at the sensing surface arising from a variety of chemical interactions. This type of configuration was applied to the understanding of vapor sensors and the effect of receptor polarity on the detection of brain injury biomarker proteins. New details about the mechanisms for sensor responses to analytes can be obtained from remote gate configurations, including connection of interfacial voltages and charge densities in responsive polymer semiconductors.
Photoactive Bimetal Cobaltite (XCo2O4: Ni, Mn, Fe, Co) Hollow-Nanofibers As an Efficient Bifunctional Photo-Electrocatalyst Towards Oer/ORR at the Cathode in Zn-Air Batteries
Authors: Tomon Chanikarn , Sarawutanukul Sangchai , Phattharasupakun Nutthaphon , Duangdangchote Salatan , Kidkhunthod Pinit , Sawangphruk Montree
Published: July 2021

Using the photo-electrocatalysts to facilitate the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) for enhancement of the Zn-air batteries (ZABs) performance has not yet been widely investigated. This work presents for the first-time bimetal cobaltites with hollow nanofiber (XCo2O4-HNF or XCO-HNF where X=Ni, Mn, Fe, or Co) morphology as photocathodes in ZABs. Among XCO-HNF, the NiCo2O4 hollow nanofiber (NCO-HNF) exhibits superior performances with the lowest overpotential (ƞOER = 306 mV at 10 mA cm2, ƞORR = 454 mV at E1/2) and highest Tafel slope of 77.3 and 63.4 mV/dec for OER and ORR, respectively. Their catalytic activities of XCO-HNF catalysts are fundamentally investigated by their band structure through a complete energy diagram constructed from the combination of UV-Vis spectroscopy, Mott-Schottky, and DFT calculation. Importantly, the photo-electrocatalytic mechanism is proposed by photogenerated electrons/ hole (NCO*) and the reducing of energy barrier in potential drop region. The NCO-HNF decreases the OER and ORR overpotentials for 14.3% and 8.1% and improves the OER and ORR kinetics for 19.3% and 20.8% compared with NCO-HNF under dark. The In-situ XAS results also reveal that light can enhance both Ni and Co catalytic activities, but Ni is found to be the main active species for OER. The as‐fabricated ZAB with the NCO-HNF photocathode exhibits the decreasing in voltage gap from 0.85 V (Dark) to 0.64 V (Light) due to the highly active NCO* hole and the excited electron transferred to reduce the ZnO to Zn at the anode. In addition, NCO-HNF under light can increase the specific capacity up to ca. 11.4% as compared to that under dark condition. These results confirm that the integration of solar energy conversion (photo-electrocatalysts) and metal-air batteries will pave the way to a sustainable development in energy storage.

Figure 1
(Invited) New Design Rules of Gas Sensors Enhance Their Reliability for End-User Acceptance
Authors: Potyrailo Radislav
Published: July 2021

Contemporary gas monitoring scenarios for industrial safety, environmental surveillance, medical diagnostics, personal wellness, and other applications demand sensors with higher accuracy, enhanced stability, and often lower power; all in unobtrusive formats and at low cost [1]. Unfortunately, available sensors based on traditional detection principles often have not only inadequate accuracy and stability but also have relatively high power demands, pushing the limits of existing detection concepts where we are reaching their fundamental performance limits. These limitations of available sensors drive the innovative designs of new generation of sensors.

This talk will stimulate your senses by (1) posing fundamental questions on principles of gas sensing and (2) by demonstrating on how modern multidisciplinary research addresses these questions by building sensors with previously unthinkable capabilities.

We will present new sensor-design criteria that allow high sensor stability and multi-gas detection with individual sensors. We brought new gas-sensing capabilities to very popular semiconducting metal oxide (SMOX) materials by introducing our dielectric excitation scheme of these materials, which is a contemporary alternative to classic resistance measurements from 1960-s [2]. Our excitation scheme based on contemporary electronics brought highly desired features such as linear sensor response (R^2 > 0.99), dynamic range of six decades of gas concentrations, 50-fold improvement in the limit of detection, and cancelled effects from ambient temperature over - 25 to 50 oC. We lab-tested our excitation scheme with numerous volatiles and did field validations in wireless sensor network, drone-based, and wearable formats. We launched a product with one of our partners and are working toward diverse consumer, industrial, medical, homeland security, and other applications.

We will conclude with a perspective for future needs and with the 2050 roadmap for ubiquitous gas monitoring.

[1] Potyrailo, R. A. Multivariable sensors for ubiquitous monitoring of gases in the era of Internet of Things and Industrial Internet, Chem. Rev. 2016, 116, 11877–11923.

[2] Potyrailo, R. A.; Go, S.; Sexton, D.; Li, X.; Alkadi, N.; Kolmakov, A.; Amm, B.; St-Pierre, R.; Scherer, B.; Nayeri, M.; Wu, G.; Collazo-Davila, C.; Forman, D.; Calvert, C.; Mack, C.; Mcconnell, P. Extraordinary performance of semiconducting metal oxide gas sensors using dielectric excitation, Nat. Electron. 2020, 3, 280–289.
Assembling an All-Solid-State Ceramic Battery: Assessment of Chemical and Thermal Compatibility of Solid Ceramic Electrolytes and Active Material Using High Temperature X-Ray Diffraction
Authors: Bertrand Marc , Rousselot Steeve , Aymé-Perrot David , Dolle Mickael
Published: July 2021

Lithium ion batteries (LIBs) are the most known and used batteries for portable energy storage because of their high energy densities, long cycle life and relatively low price. However, they still fall short for the development of long range electric vehicles and stationary applications due to organic liquid electrolytes that are currently electrochemically limited and present safety issues (fire or explosion in case of short-cut or overcharging). Solid oxide electrolytes appear to be one of the solutions because of their non-flammability and wide potential window. Inorganic oxide electrolytes have reasonable ionic conductivities (10-5-10-3 S/cm at ambient temperature), high mechanical strength, and high chemical stability.

Assembling an all ceramic solid-state battery with inorganic oxide electrolyte is challenging as it requires a deep knowledge of the thermal, chemical and electrochemical behavior of each component of the cell. The battery must be a continuous monolithic block with a thin dense electrolyte separator, in order to minimize the polarization. In addition, optimized interfaces between active material and electrolytes must be ensured in the composite electrodes. This is often achieved with oxide-based materials by using high temperature processing.

Thermal expansion occurring during this step can lead to cracks, which will affect the performance and cyclability of the device. The primary driving force of a crack during the fabrication of hybrid ceramic is the stress due to mismatch in the coefficient of thermal expansion (TEC) of the various layers/materials. Moreover, it must be certain that no reaction occurs between active material and electrolytes in the sintering temperature range. These are then two key parameters to address for the development of all ceramic solid-state batteries.

In this work, in situ-XRD has been used to determine the TEC and the thermal stability of various well-known oxide active materials and solid electrolytes. The aim of this presentation is to discuss about the best selection of compatible oxide-based materials to avoid unwanted cracks or reaction during the sintering processing of ceramic solid-state batteries.
Shape-Memory Solid Polymer Electrolytes
Authors: Jabbari Vahid , Shahbazian-Yassar Reza
Published: July 2021

Stimuli-responsive materials are smart materials capable to adjust their properties (e.g. shape and size) in response to an external or internal stimulus including temperature, light, magnetic field, mechanical stress, and pH. Shape memory polymers (SMPs) are attractive class of stimuli-responsive, programmable smart materials with shape-memory behavior: memorize their original, permanent shape; deform and fix into a secondary, temporary shape; and recover the original, permanent shape upon applying an external stimulus. In recent years, advancing intelligent supercapacitors and batteries have attracted significant attention whereas stimuli-responsive materials were integrated to induce stimuli-responsive properties to introduce new properties or mitigate some of the existing issues such as thermal management, mitigating volume change-induced performance degradation, recovery from a mechanical deformation, self-healing, electrochromism. Indeed, integrating energy storage technologies with a variety of stimuli are a fascinating method to realize smart functions [1-3].

Herein, we aim to develop a heat-responsive battery capable of mitigating the impact of incidental mechanical abuse or deformation. To achieve this, a shape-memory solid polymer electrolyte (SMSPE) is engineered and incorporated into lithium metal batteries (LMBs). In response to an external heat, the engineered SMSPEs recover their original shape and size from mechanical deformations such as bending and elongation. This study opens-up a promising approach for engineering intelligent batteries responsive to unfavorable internal or external stimuluses, with potential to have a broad impact on other energy storage technologies in different sizes and shapes. The Li|SPSPEs|LFP full cell batteries display a long-term cycle life with a discharge capacity of ~120 mAh g−1 at C/10 in ambient temperature with around 90% capacity retention after 100 cycles. Moreover, the Li|SPSPEs|Li symmetrical cells exhibit a long-term stability with a low voltage polarization at a current density of 0.05 mAh cm−2 for up to 1000 cycles.

Overall, the proposed approach shows a promising design principle which can open up new possibilities for the next-generation batteries and their safe operation. With vast range of available SMPs with tunable chemistries, transition temperatures, and high shape-memory performance, and opens up new frameworks to address a variety of detrimental, unresolved issues such as thermal runaway, with potential expansion to the other energy storage technologies.

References:

C. D. Wick, A. J. Peters, G. Li, Quantifying the contributions of energy storage in a thermoset shape memory polymer with high stress recovery: a molecular dynamics study, Polymer, 2020, 123319.

Y. Meng, J. Jiang, M. Anthamatten, Body temperature triggered shape‐memory polymers with high elastic energy storage capacity, 2016, 54, 1397-1404.

H. Zhou, H. Luo, et al., Healable, Flexible Supercapacitors Based on Shape Memory Polymers. Appl. Sci. 2018, 8, 1732.
New Cathode and Electrolytes Strategies to Enable High-Energy Li-S Batteries
Authors: Xu Guiliang , Amine Khalil
Published: July 2021

Lithium–sulfur batteries are attractive alternatives to lithium-ion batteries because of their high theoretical specific energy and natural abundance of sulfur. However, the polysulfides shuttle and the Li metal dendrite and corrosion significantly limit their cycle life. Moreover, the poor electronic conductivity of sulfur results in low areal sulfur loading and poor utilization, leading to low overall specific energy.

In the past years, we have developed several new strategies to mitigate these probelms, including: (1) Se doing because of much higher electronic conductivity of Se than Sulfur;[ref 1] (2) new electrolytes to directly bypass polysulfides formation and enable reversible Li stripping/plating;[ref 2 and 3]; (3) rational cathode design to boost sulfur reaction kinetics and suppress polysulfides shuttle and Li corrosion (ref 4 and 5). Through these approaches, we have significantly improve the cycle life and specific energ of Li-S batteries in both coin-cells and pouch-cells.

Ref:

[1] Xu, G. L.; Ma, T.; Sun, C. J.; Luo, C.; Cheng, L.; Ren, Y.; Heald, S. M.; Wang, C.; Curtiss, L.; Wen, J.; Miller, D. J.; Li, T.; Zuo, X.; Petkov, V.; Chen, Z.*; Amine, K.*, Insight into the Capacity Fading Mechanism of Amorphous Se2S5 Confined in Micro/Mesoporous Carbon Matrix in Ether-Based Electrolytes. Nano Lett.,
2016, 16, 2663-2673.

[2] Xu, G. L.; Sun, H.; Luo, C.; Estevez, L.; Zhuang, M. H.; Gao, H.; Amine, R.; Wang, H.; Zhang, X.; Sun, C. J.; Liu, Y. Z.; Ren, Y.; Heald, S.; Wang, C. S.; Chen, Z.*; Amine, K.*, Solid-State Lithium/Selenium-Sulfur Chemistry Enabled via a Robust Solid-Electrolyte Interphase. Adv. Energy Mater.,
2018, 1802235.

[3] Amine, R.; Liu, J.; Acznik, I.; Sheng, T.; Lota, K.; Sun, H.; Sun, C. J.; Fic, K.; Zuo, X.; Ren, Y.; EI-Hady, D. A.; Alshitari, W.; Al-Bogami, A. S.; Chen, Z.; Amine, K. (*) and Xu, G. L. (*). Regulating the Hidden Solvation-Ion-Exchange in Concentrated Electrolytes for Stable and Safe Lithium Metal Batteries. Adv. Energy Mater.,
2020, 2000901.

[4] Zhao, C.; Xu, G. L.(*); Zhao, T. (*); Amine, K.(*). Beyond Polysulfides Shuttle and Li Dendrite Formation: Addressing the Sluggish S Redox Kinetics for Practical High Energy Li-S batteries. Angew. Chem. Int. Ed.
2020, 17634-17640.

[5] Zhao, C.; Xu, G. L.(*); Yu, Z.; Zhang, L.; Hwang, I.; Mo, Y.-X.; Ren, Y.; Cheng, L.; Sun, C. -J.; Ren, Y.; Zuo, X.; Li, J.-T.; Sun, S.-G.; Amine, K.(*) and Zhao, T.(*). A high-energy and long-cycling lithium-sulfur pouch cell via a macroporous catalytic cathode with double-end binding sites. Nature Nanotechnology, 2020, https:// doi .org/ 1 0 . 1 0 3 8 / s 4 1 5 6 5 - 0 2 0 - 0 0 797-w.
Tungsten Oxide Nanowire/Carbon Nanotube Interlayer As a Polysulfide Mediator for High-Performance Lithium-Sulfur Batteries
Authors: Kim Hun , Sun Yang-Kook
Published: July 2021

In this study, we designed a new nanaowire to enhance the performance of lithium-sulfur batteries. Tungsten oxide nanowires (WNWs) were synthesized via a simple hydrothermal method. WNWs and one-dimensional materials easily mix with carbon nanotubes (CNTs) to form interlayers. The WNW interacts with lithium polysulfides as a thiosulfate mediator by positioning the lithium polysulfide near the cathode to increase the reaction kinetics. The lithium-sulfur cell with WNW/CNT interlayer achieves a very high initial discharge capacity of 1558 mAh g-1 and 656 mAh g-1 at 0.1 C and 3 C, respectively. Moreover, a cell with a high sulfur mass loading of 4.2 mg cm-2, still delivers a high capacity of 1136 mAh g-1 at a current density of 0.2 C. This excellent performance and structural stability are due to the chemical adsorption and catalytic effects of the thiosulfate mediator on WNW.

References

Hwang, J.-Y.; Kim, H. M.; Shin, S.; Sun, Y.-K., Adv. Funct. Mater. 2018, 28, 1704294.

Lin, H. B.; Zhang, S. L.; Zhang, T. R.; Ye, H. L.; Yao, Q. F.; Zheng, G. W.; Lee, J. Y., Adv. Energy Mater. 2018, 8, 1801868.

Kumar, R.; Liu, J.; Hwang, J.-Y.; Sun, Y.-K., J. Mater. Chem. A 2018, 6, 11582-11605.
Investigating Molten Sodium Batteries with an Aqueous Catholyte
Authors: Gerbig Felix , Nirschl Hermann
Published: July 2021

High-temperature liquid sodium batteries (e.g. sodium-sulfur) are a well-established technology for large-scale grid storage. Combining the molten sodium anode with an aqueous iodine cathode overcomes the problems of thermal loses and sealing by reducing the operating temperature to about 100°C.

This leads to higher cost efficiency, energy density and a simplified cell design. Due to their sustainability and high efficiency, which is comparable to Li-Ion –batteries, mid-temperature sodium-iodine batteries are a promising candidate for small and medium scale stationary energy storage applications. Experiments performed by Holzapfel et al. show proof of principle for a current density of 20 mA cm-2 (55mW cm-2) up to a maximum current density of 100 mA cm-2 (180mW cm-2)[1] . The used iodine concenctrations correspond to 405 Wh l-1 on catholyte basis or a very high specific energy of 198 Wh kg-1 including anolyte and catholyte. Sodium-iodine batteries have the ability to meet the growing demand of short-term energy storage caused by the integration of renewable energy sources into the power grid.

Although these batteries are theoretically described in literature, the detailed processes inside the battery are not well understood[2] . Quantities like initial species concentrations, C-rate, cell design and cathode geometry have large impacts on the overall battery performance. Simulations have to be undertaken because experimental studies are limited to macroscopic quantities like external current or electric potential. Here we present a fully resolved 3D simulation model developed from a LIB simulation tool[3] to gain insight into microstructural processes inside the battery.

The proposed spatially resolved three-dimensional model takes charge and mass transport, heterogeneous and homogeneous reactions as well as the electrochemical processes into account. In this contribution, we present recent investigations about cell design, cathode material structures and the electrolyte composition carried out with a new 3D simulation model.

A deeper understanding of these processes is inevitable for enhancing the battery performance by choosing the optimal above-mentioned quantities.

Figure 1