bluuebunny/crossref_metadata_2025_split huggingface dataset:
Numerical Model of an Enzymatic Glucose Sensor with a Blocking Layer on the Electrode
Authors: Jacobs Samuel , Miller Michael , Batmanghelich Farhad , Orazem Mark E. 
Published: November 2022

Glucose oxidase-based biosensors are a primary method for continuous glucose monitoring. b-glucose reacts with immobilized glucose oxidase to form gluconic acid and hydrogen peroxide. Hydrogen peroxide is oxidized on an adjacent electrode. The resulting anodic current is proportional to the concentration of glucose. The measured current may be influenced by oxidation of secondary species, such as ascorbic acid and acetaminophen, or fouling of the sensor via foreign body response.[1-3] A blocking layer, placed between the electrode and the immobilized enzyme layer, may act to prevent diffusion of secondary species to the electrode, and reduce the influence of the foreign body response.[3]
The influence of a blocking layer on the steady and transient operation of the sensor was evaluated numerically. A blocking layer was added to the steady and transient glucose sensor model outlined in previous work [4] to address the potential influence of acetaminophen. Sensor performance was evaluated for multiple blocking layer thicknesses, reacting species diffusion coefficients, and oxygen concentration. The polarization behavior of the sensor was modeled. Selectivity to glucose was improved by addition of a blocking layer, but sensitivity to oxygen was increased with increasing blocking layer thickness.
Numerical simulations of the transient response to a step change in glucose for a sensor with the blocking layer had a response time comparable to the response without the blocking layer, except when the hydrogen peroxide diffusion was greatly reduced in the blocking layer. A step change in acetaminophen yielded time constants comparable to that of the glucose step change in the absence of a blocking layer. The results are sensitive to the thickness of the blocking layer and to the diffusivity of the interfering species in the blocking layer.
References

Basu, A., & Veettil, S. (2016). Direct Evidence of Acetaminophen Interference with Subcutaneous Glucose Sensing in Humans: A Pilot Study. Diabetes Technology & Therapeutics, 18(S2), 43-47.

Surani, S., & Sharma, M. (2021). Interaction between vitamin C and point of care glucose monitoring. Are we overly wary of it or is it a valid concern? Current Medical Research and Opinion, 37(7), 1111-1113.

Yang, Y., Zhang, S., & Kingston, M. (2000). Glucose sensor with improved haemocompatibility. Biosensors and Bioelectronics, 15, 221-227.

Jacobs and M. E. Orazem, ``Transient Response of a Continuous Glucose Monitor," presented at the 240th Meeting of the Electrochemical Society, Orlando, Florida, October 10-14, 2021.

Acknowledgement
The support of Medtronic Diabetes (Northridge, CA) is gratefully acknowledged.
(Invited) Hydrogen Assisted Carbonate Electrolysis for Direct Air Capture of CO2
Authors: Lattimer Judith , Kastelic Matthew , McCatty Steve 
Published: November 2022

Reduction of greenhouse gases is vital for the long-term environmental health of the planet. While there has been progress in reducing CO2 emissions at large point sources, a significant portion of the CO2 emitted each year in the United States is released from distributed sources, like cars, smaller factories, and farms. Direct capture of CO2 from ambient air is therefore necessary for the ultimate reduction of greenhouse gas emissions in the atmosphere. However, capturing the CO2 in ambient air presents a much greater challenge due to the dilute nature of the CO2, requiring different strategies than carbon capture from concentrated CO2 waste streams.
We are developing a novel process for the capture and containment of CO2 from air into a purified, concentrated CO2 stream that can be redirected for use as a feedstock for a wide variety of applications, including chemical manufacturing and syngas formation. This process involves the capture of CO2 in a concentrated KOH solution using a high-surface area air contactor to form potassium carbonate. The potassium carbonate is then efficiently electrolyzed in a hydrogen-assisted process to regenerate the CO2 at a low operating potential, increasing the electrical efficiency of the process while producing concentrated and purified CO2. In addition, water, hydrogen, and KOH are also regenerated as byproducts that can be recycled back into the CO2 capture and electrolysis processes, reducing both overall energy and chemical consumption.

Using a custom designed test stand and traditional electrolysis cell design, we have demonstrated voltage of <1.8 V at 100 mA/cm2 for potassium carbonate conversion to carbon dioxide at the anode, with concomitant H2 and KOH production at the cathode, based on potassium-selective ion exchange across the membrane. Furthermore, using a custom 3-compartment electrolysis flow cell and ion-selective membranes, we successfully demonstrated hydrogen-assisted carbonate electrolysis, with hydrogen consumption at the anode, hydrogen and KOH production at the cathode, and CO2 formation from potassium carbonate in an internal flow-through compartment, at 1.4 V at 50 mA/cm2. Further improvements in operating conditions and cell components and design should decrease the operating voltage significantly, to <1 V at 100 mA/cm2.

Acknowledgement: The project is financially supported by the Department of Energy’s ARPA-E Office under the Grant DE-AR0001495
Design Principles for Flow Batteries: Cation Dependent Membrane Resistance and Active Species Solubility
Authors: Waters Scott E. , Thurston Jonathan R. , Armstrong Robert W. , Robb Brian H. , Marshak Michael , Reber David 
Published: November 2022

Aqueous redox flow batteries are generally adapted from polymer electrolyte membrane fuel cells that use proton exchange membranes to balance the charge of the cell. Such membranes are well understood and exhibit excellent performance in acidic electrolytes via transport of protons. For neutral pH flow batteries however, the primary cation in solution is not H+, but the cation of the active material or supporting electrolyte salt.
The nature of the cation in solution, e.g., hydrated ionic radius and charge density, significantly affects the transport resistance through the membrane and thus the area specific resistance of the cell, a critical parameter that needs to be minimized for high power applications such as flow batteries. Additionally, different cations result in vastly different solubilities of active materials based on redox active anions such as ferrocyanides; the ammonium salt for example is ca. three times more soluble than the sodium salt (1.6 M vs. 0.5 M).[1] It is therefore critical to not only maximize the concentration of an electrolyte and thus its capacity, but to also choose cations that enable efficient transport across the membrane for efficient flow battery development.
Here, we study the cation dependent resistance of NafionTM 212 cation exchange membranes for 12 different alkali and alkylammonium cations and determine the solubilities of 13 ferrocyanides as well as 35 metal-organic chelates based on aminopolycarboxylate ligands. The latter are a particularly promising family of compounds for application in negative electrolytes in near neutral pH aqueous flow batteries with demonstrated discharge voltages as high as 2.1 V and excellent power performance.[2] We further discuss cation-compatibility for mixed cation electrolytes as well as membrane pretreatments that affect the cells area specific resistance and active species crossover.[3]

References:

[1] J. Luo, B. Hu, C. Debruler, Y. Bi, Y. Zhao, B. Yuan, M. Hu, W. Wu, T.L. Liu, Unprecedented capacity and stability of ammonium ferrocyanide catholyte in pH neutral aqueous redox flow batteries, Joule
2019, 3, 149–163.

[2] B.H. Robb, J.M. Farrell, M.P. Marshak, Chelated chromium electrolyte enabling high-voltage aqueous flow batteries, Joule
2019, 3, 2503–2512.

[3] S.E. Waters, J.R. Thurston, R.W. Armstrong, B.H. Robb, M.P. Marshak, D. Reber, Holistic design principles for flow batteries: Cation dependent membrane resistance and active species solubility, J. Power Sources
2022, 520, 230877.
Modeling Electrochemical Transport within a Three-Electrode System Towards Fast Charge Applications
Authors: Garrick Taylor R. , Gao Jing , Koch Brian 
Published: November 2022

In support of GM's traction battery efforts, we derive and implement a method to describe the electrochemical performance of a battery cell through the combination of a modified Newman Pseudo 2-Dimensional model and a three-electrode experimental apparatus. To assess the capability of the method, we compare model results with experimental data for a lithiated graphite and lithium nickel manganese cobalt oxide system. The model is applied to simulate the electrochemical and transport processes within the battery cell to predict the negative electrode potential and positive electrode potential with respect to a lithium iron phosphate reference electrode, as well as the terminal voltage. We extend this discussion to cover applicability to fast charge considerations to avoid lithium plating at the anode during a fast charge event.
References:
1. Taylor R. Garrick, Jing Gao, Xingyi Yang, and Brian J. Koch. 2021 J. Electrochem. Soc. 168 010530
(Invited) State of Charge Monitoring of Vanadium Flow Batteries Using Spectroscopic and Electrochemical Methods
Authors: Rybalchenko Maria , Quill Nathan , Buckley D. Noel , Lynch Robert P. 
Published: November 2022

Vanadium Flow Batteries (VFBs) are a promising energy storage technology, particularly for large and medium scale applications. In a VFB, energy is stored in two vanadium electrolytes separated by a nafion membrane. The use of vanadium electrolytes in both half-cells minimises cross contamination issues which have plagued other flow battery chemistries. The electrodes, electrolytes and membrane are key areas of research for VFBs with the aim of improving efficiency, energy density and costs.
Accurately monitoring state-of-charge (SoC) is vital for any rechargeable battery system. It is important to monitor the SoC of both half-cells simultaneously because of imbalances which occur due to side reactions and unwanted vanadium transfer across the membrane. The electrolyte may be rebalanced by various techniques but only if the SoC of each half-cell is accurately known. There are multiple possible techniques to monitor the SoC of each half-cell. We measure SoC in-situ by analysing the absorbance spectra of the vanadium electrolytes as they are charged and discharged. We also accurately measure volume changes throughout the cycle to study the water transfer through the nafion membrane. This accurate SoC data which is obtained will be compared with other SoC techniques. It will also be used to study the performance characteristics of the battery.
Acknowledgements:
This research was funded by the Sustainable Energy Authority of Ireland (Award Number 18/RDD/341).
(Invited) Gas Phase Coating of Particles for Energy Applications
Authors: van Ommen J. 
Published: November 2022

Advanced materials, often relying on nanostructured particles as building blocks, are crucial in meeting grand challenges in energy: battery materials, electrocatalysts, phase change materials, etc. etc. Gas phase deposition techniques, such as chemical vapour deposition (CVD), atomic layer deposition (ALD), and molecular layer deposition (MLD) are excellent methods to make such nanostructured particles: particles of which the surface is either covered by an ultrathin film or by nanoclusters. When combined with proper particle handling, these coating methods are also very well suitable for scaling up. This requires adequate reactor technology to optimize the contacting of particles and gaseous reactants.
Gas phase coating such as CVD and ALD is already widely applied in the semiconductor industry. Although the underlying mechanisms are similar, there are quite some differences between gas phase deposition on wafers and coating particles. This tutorial will discuss recent developments and insights in the field of applying gas phase deposition to particles, with an emphasis on reactor technology, precursor utilization, operating conditions, and scaling up. I will show that we can produce nanostructured particles with very high precision in a scalable way. I will focus on energy applications, and will discuss how this approach can also be of value in light of the increasing demand for critical raw materials.
Unveiling Hidden Chemistry between an Aluminum ALD Precursor and Li Metal Anodes
Authors: Kang Donghyeon , Mane Anil U. , Elam Jeffrey W. 
Published: November 2022

Trimethylaluminum (TMA) is a widely utilized aluminum precursor for atomic layer deposition (ALD) in various aluminum-based coatings. For example, TMA produces Al2O3 with H2O,[1] AlF3 with HF-pyridine,[2] and Al2S3 with H2S [3] with well-defined ALD mechanisms. These ALD processes have been widely applied into various materials to introduce ultra-thin Al-based coating layers, including energy storage materials such as battery cathodes, anodes, and solid electrolytes. Our group demonstrated that the Al2O3 ALD process using TMA can be used for Li-metal anode coating to improve electrochemical stability and reduce Li-dendrite formation during battery cycling.[4]
Although many studies about ALD on Li metal anodes have been reported using TMA, most of them focus on Li-metal battery performance, instead of ALD chemistry. During deep investigation on ALD chemistry of TMA, we recently discovered an interesting chemistry between TMA and reactive metal substrate (i.e. Li metal). Based on our observation, TMA reacts with Li-metal during ALD cycles then producing a carbon composite layer on the top of Li metal, not following conventional ALD mechanisms. It may come from highly reactive nature both of TMA and Li metal. Despite of wide use of TMA, this phenomenon has not been reported to date because Li metal is passivated by several layers such as Li2CO3, LiOH and Li2O even stored in glovebox environment. In this presentation, we will discuss the chemistry between TMA and Li metal found by in-situ QCM, high-resolution XPS, SEM, and Raman studies. Then we will also demonstrate how this unexpected ‘side reaction’ can be utilized in Li-metal battery applications using liquid and solid electrolytes.
[1] 1. A. C. Kozen et al., ACS Nano, 9, 5884–5892 (2015).
[2] Y. Lee, H. Sun, M. J. Young, and S. M. George, Chemistry of Materials, 28, 2022–2032 (2016).
[3] X. Meng, Y. Cao, J. A. Libera, and J. W. Elam, Chemistry of Materials, 29, 9043–9052 (2017).
[4] L. Chen et al., Journal of Materials Chemistry A, 5, 12297–12309 (2017).

Figure 1
Atomic Layer Deposition of Metal Phosphates
Authors: Henderick Lowie , Dhara Arpan , Werbrouck Andreas , Dendooven Jolien , Detavernier Christophe 
Published: November 2022

Since the introduction of lithium iron phosphate (LFP) as an electrode material for Li-ion batteries (LIB’s), metal phosphates in general have become increasingly important. The strong covalency of the P-O bonds typically results in a very good thermal and structural stability, which is one of the main reasons for the success of LFP as a LIB electrode. However, the applications of these metal phosphates are multi-fold. Apart from LIB’s, they have been proven to be promising towards e.g. electrocatalytic water splitting, biocompatible coatings or even as protective coatings for luminescent materials.
With these applications in mind, the research towards the deposition of these materials also becomes increasingly important. Atomic Layer Deposition (ALD) has emerged as a deposition technique with unique nanotailoring capabilities compared to conventional methods, particularly owing to its high thickness and compositional control. Down-scaling micro-electronic devices according to Moore’s law has already increased interest in the unique capabilities ALD can offer. However, in addition to using ALD for the fabrication of such devices, it can also offer a unique way to create model systems to gain a fundamental insight for a broad range of applications.
From this it can be seen why the combination of both research fields, i.e. ALD of metal phosphates, is gaining a lot of interest over the past years. Since the first metal phosphate has been deposited in 1969, a big challenge has been to find a suitable phosphate precursor. Today, the most popular choice proves to be trimethyl phosphate, i.e. TMP. It has allowed for the deposition of a variety of phosphates (e.g. aluminium phosphate, lithium phosphate, iron phosphate, etc.), but more research is required to further extent this research field. To stimulate this research, a comprehensive study on the currently (un)available literature is needed. It would e.g. allow to get a better understanding on the effect of different phosphate precursors and/or various reaction mechanisms during ALD can be better understood, as well as the potential applications of these materials (such as lithium ion battery applications). As such a study on ALD of metal phosphates was so far not yet available, we hope that this work can create a view that is of interest towards various scientific fields, and help to guide future thin film researchers.
(Digital Presentation) Design of High Barrier Property and Flexible Inorganic/Polymer Hybrid Film for Encapsulation of Flexible Electronics
Authors: Wen Di , Zhang Yinghao , Li Yun , Yang Fan , Chen Rong 
Published: November 2022

Designing encapsulation film with both high barrier property and excellent flexibility has been challenging for the current brittle inorganic films owing to the strain-induced cracking. Inorganic/organic multilayer has been proposed due to the organic layer can function as buffers of the inorganic layer and defect-decoupling layer, realizing the improvement of flexibility and maintaining barrier property. Polydimethylsiloxane (PDMS) was widely used as an organic encapsulation layer due to its high stability, elasticity, and transparency. The introduction of PDMS helps the barrier film to resist distorting under the bending motions. However, the delamination and cracking occurred under bending motion in a small curvature radius due to the mismatched strain and coefficient of thermal expansion (CTE) between PDMS and inorganic films such as Al2O3. Realization of improving their strain and CTE mismatch is possible by doping nanoparticles into PDMS. The Al2O3/PDMS hybrid film with the doping of SiO2 fabricated via atomic layer infiltration (ALI) method showed mechanical stability and endure 1000 repetitive stretch tests with 1%, but the water vapor transmission rate (WVTR) was only 10-3 g/m2/day, which was attributed to the lower crosslinking density of PDMS result in higher free volume and chain mobility. It’s a challenge to develop a strategy for improving the crosslink density of PDMS. In this work, the PDMS-based composite substrate with engineered stiffness was developed by employing the addition of silane coupling agent and SiO2. Atomic layer infiltration (ALI) coupled with UV-curing was introduced for sub-surface cross-linking of PDMS in Al2O3/SiO2/PDMS hybrid film, and the resulted Al2O3/SiO2/PDMS hybrid film showed highly stretchable and barrier properties. The result indicates that Al2O3/SiO2/PDMS hybrid film is a promising encapsulation film applicable to flexible electronics.
Keywords: atomic layer infiltration (ALI), flexible film, encapsulation, UV-curing method, water vapor transmission rate (WVTR)
Refs.

Y. Li, D. Wen, Y. Zhang, Y. Lin, K. Cao, F. Yang, R. Chen, Highly-stable PEN as a gas-barrier substrate for flexible displays via atomic layer infiltration, Dalt. Trans. (2021) 16166–16175. https://doi.org/10.1039/d1dt02764f.

Zhang, D. Wen, M. Liu, Y. Li, Y. Lin, K. Cao, F. Yang, R. Chen, Stretchable PDMS Encapsulation via SiO2 Doping and Atomic Layer Infiltration for Flexible Displays, Adv. Mater. Interfaces. 9 (2022) 1–9. https://doi.org/10.1002/admi.202101857.
(Digital Presentation) Understanding of Single-Crystal Fabrication of High-Nickel Layered Oxide through Variation of Heating Process
Authors: Fung Kuan-Zong 
Published: November 2022

Single-crystal processing of layered oxide cathode has received great attention recently. It has been recognized that Ni-rich layered oxide with grain size in mm range tends to provide better cycling performance due to better structural integrity against volume changing during charge/discharge cycles.
However, during heating/calcination process of oxide/carbonates/nitrates powder compacts, it may involve decomposition, chemical reactions, diffusion, oxidation, sintering, grain-growth.
For grain growth to take place at final stage of sintering, the powder compacts need to be heated to higher temperatures for certain period of time. On the other hand, the formation of Ni-rich layered oxides need air/oxygen for Ni oxidation and better crystallization. Thus, it is crucial to investigate the processing of single-crystal Ni-rich layered oxide based on the sintering behavior, thermal gravimetric analysis, and phase transformation. Furthermore, the lithiation/oxidation of Ni-containing oxides during single-crystal processing may involve charge compensation resulted from defect reactions. In this study, the affected electrical, optical, structural, and electrochemical properties of layered oxides will be discussed based on defect chemistry consideration. The structural, microstructural and electrical properties of decomposed precursors and doped layered oxides will be examined using XRD, SEM and DC/AC impedance measurements. CV and charge/discharge tests from assembled coin cells will be used to evaluate electrochemical properties of single-crystal Ni-rich layered oxides.
Ligand Elucidation of Dissolved Transition Metal Ions in Pristine and Degraded Electrolytes in Li-Ion Batteries
Authors: Szczuka Conrad , Allen Jennifer P. , Jakes Peter , Grey Clare P. , Eichel Rüdiger-A. , Granwehr Josef 
Published: November 2022

During operation of a Li-ion battery, layered transition metal oxides release metal ions into the electrolyte. In addition to capacity loss, dissolved metal ions are mobile in the electrolyte and can deposit at the anode, enhancing Faradaic losses and posing the risk of dendrite formation.[1] In the electrolyte solution, transition metal ions are characterized mainly by their oxidation state and complexation behavior, which dictate the transport through the electrolyte. Additionally, mechanistic insights, indirect information about electrolyte degradation, and design of counter-measures might be extracted thereof. However, particularly the coordination sphere is difficult to access, due to inherently low concentrations and scarcity of suitable analytics.
In this work, the coordination sphere of dissolved transition metal ions is selectively probed by pulse Electron Paramagnetic Resonance (pEPR). pEPR selectively addresses isolated paramagnetic ions, masking analytical interference from other species in the battery. Because of its known impact on capacity fade, firstly Mn2+ is analyzed in premixed pristine and degraded electrolyte solutions. Carbonates with high dielectric constants such as ethylene carbonate (EC) are the dominant ligands, accompanied by electrolyte salt anions for charge compensation. If present, trace amounts of electrolyte degradation products such as fluorophosphates selectively form the first coordination sphere. The results from pEPR measurements, that have to be performed on frozen solutions at cryogenic temperatures, agree with paramagnetic NMR results at ambient temperatures. Furthermore, samples from batteries operating with vanadium-based cathodes were investigated. Depending on the storage conditions, V4+ ligands predominantly consist of decomposition products from the electrolyte solvent ethylene carbonate (e.g. ethylene glycol anions) or electrolyte salt LiPF6 (fluorophosphates).[2,3]

[1] C. Zhan, T. Wu, J. Lu, K. Amine, Energy Environ. Sci.
2018, 11, 243–257.
[2] C. Szczuka, R.-A. Eichel, J. Granwehr, ACS Appl. Energy Mater.
2022, 5, 449–460.
[3] C. Szczuka, P. Jakes, R.-A. Eichel, J. Granwehr, Adv. Energy Sustain. Res.
2021, 2, 2100121.