bluuebunny/crossref_metadata_2025 huggingface dataset:
(Digital Presentation) A 2.8V Reversible Sn-Li Battery
Authors: Xue Kaiming , Yu Denis
Published: July 2022

Tin (Sn) is a metal that is commonly used in our daily life. With the rapid development of lithium-ion battery in the past decades, Sn and its alloy, such as Sn-Cu[1], and Sn-Ni[2], Sn-Co[3] and Sn-Fe[4] have been used as anode for lithium-ion battery because they can undergo alloying/dealloying process with lithium ions and exhibit high capacity and suitable working voltage of about 0.4 V vs. Li/Li+. Sn can also undergo an oxidation reaction to Sn2+, with an electrode potential of about -0.14 V vs. SHE. It is therefore possible to also use Sn as a cathode material.

Herein, we are first to demonstrate a metal-metal battery made up of Sn metal as the cathode and Li metal as the anode in organic electrolyte (see Fig. a). Sn foil and Li foil are simply assembled with 3M LiTFSI in dimethoxyethane/propylene carbonate (DME/PC) electrolyte in an Ar-filled glove box to form a pouch cell. During charging, Sn will give out two electrons and dissolves into the electrolyte as Sn2+, while during discharging, the metal ions will be re-deposited onto the cathode. Thus, the energy is stored in the form of Sn2+ in the electrolyte. The charge-discharge curves in Fig. b show that the operating voltage of the battery is about 2.8 V.

Since Sn2+ that is dissolved into the electrolyte from the cathode has higher potential than the Li metal anode, any Sn2+ ions cross-over to the anode will be spontaneously reduced, decreasing the efficiency of the battery. To suppress such self-discharge process, an anion exchange membrane based on poly(ionic liquid) polymer coated on common polypropylene separator is adopted. The Sn-Li battery with the modified separator tested in a current rate of 0.2 mA cm-2 with a capacity limitation of 0.1 mAh cm-2 gives an average Coulombic efficiency about 99.5% and can be cycled for more than 1500 cycles(See Fig. c).

We found that the stripping/deposition of Sn on the cathode, and its polarization depend strongly on the type of electrolyte used. With 3M LiTFSI in DME/PC electrolyte, the discharge voltage is lowered by about 0.05 V when the current density is increased from 0.2 mA cm-2 to 1 mA cm-2. More results on the factors affecting the charge-discharge performance of Sn-Li batteries will be discussed at the meeting.

[1]X. F. Tan, S. D. McDonald, Q. Gu, Y. Hu, L. Wang, S. Matsumura, T. Nishimura, K. Nogita, Journal of Power Sources
2019, 415, 50.

[2]H. Zhang, T. Shi, D. J. Wetzel, R. G. Nuzzo, P. V. Braun, Advanced Materials
2016, 28, 742.

[3]J. Yang, J. Zhang, X. Zhou, Y. Ren, M. Jiang, J. Tang, ACS Applied Materials & Interfaces
2018, 10, 35216.

[4]Z. Lin, X. Lan, X. Xiong, R. Hu, Materials Chemistry Frontiers
2021, 5, 1185.

Figure 1
Conducting Polymer Hybrids As Diagnostic Chemosensors
Authors: Gouma Perena , Gilmore Tessa
Published: July 2022

Polyaniline is a conducting polymer in which both redox and protonating/deprotonating conduction mechanisms are activated in the presence of gaseous compounds, making it a gas sensor. Resistive chemosensors based on PANI, in particular, have been well studied for their gas sensing properties and are considered important sensing materials for a wide range of applications as they operate at room temperature. There is, however, a novel class of polyaniline hybrids with cellulose acetate that may be suitable for detecting biomarkers emitted from the skin and in measuring the pH of breath condensate for diseases and thus, worth studying them further. This work is our perspective on the need of hybrid PANI-CA materials for use in detecting biomarkers emitted from the skin and in measuring the pH of breath condensate for diseases.
Novel Electrospinning Process for Wearable Sensors
Authors: Gilmore Tessa , Gouma Perena
Published: July 2022

Wearable electronic textiles (smart textiles) combine regular clothing with materials comprising smart sensing capabilities. As such, smart textiles have been increasingly researched across multidisciplinary fields this past decade. Applications for smart fabrics include clothing that assimilate information technologies, communication, magnetic shielding, and sensors for military and healthcare monitoring. Current smart fabrics are generally bulky, heavy weight, and uncomfortable to wear due to the use of metals for sensing and electrical connections. However, electrospinning potentially offers a new way to use polymers instead of metals to create smart textiles that are much more comfortable for the user. The purpose of this study is to obtain a three-dimensional “fluffy mass” from a smart polymeric solution via electrospinning. The mass should behave similarly to a cotton ball that then could be processed through general weaving procedures to form a yarn. The yarn could then be woven into clothing. An electrospinning collector was fabricated from extrapolated dimensions from previous literature in a half-scaled model using aluminum. Along with the collector, a variable speed, low RPM motor was constructed using commercial-off-the-shelf (COTS) parts. A high throughput setup, involving one extruder and an grounded rotating collector in a vertical configuration, generated unidirectional oriented Polyvinylpyrrolidone (PVP) fibers in a hollow casing. This same assembly has the potential to be scaled to produce smart fabrics in large quantities in short periods of time. With further experimentation such as adjustments to the motor speed and/or modifications to the collector design this study could generate an improved procedure to obtain smart materials needed for more comfortable and practical wearable electronics.
Designing N-Graphene Nanowalls Via Plasma-Enabled Nitrogen Incorporation and Substitution
Authors: Santhosh Neelakandan Marath , Cvelbar Uros
Published: July 2022

Surface engineering of graphene-based materials with nitrogen is a potential technique for tailoring the electrical and electronic features of the nanostructures. Surface engineered graphene can be fabricated by adsorbing foreign molecules into the graphene lattice or substitutional doping. Considering different chemical and physical doping techniques, plasma-assisted surface treatment is one of the fastest approaches to design nitrogen-incorporated graphene (N-graphene) with different nitrogen bonding configurations. However, it is still a great challenge to create N-graphene with controlled concentrations and desired configurations of nitrogen. Several studies demonstrated that the structural defects in graphene have a critical role in incorporating N-atoms, which has been well-explained by DFT theories. However, there is a lack of experimental studies to confirm the DFT theories explained for the influence of structural defects for nitrogen incorporation in graphene. In this study, we have demonstrated a systematic study on designing N-graphene with controlled concentration and configuration of nitrogen by plasma post-treatment on vertically oriented graphene nanowalls (GNWs). A low-pressure inductively coupled radio-frequency plasma is used for surface engineering with nitrogen gas as the reactive gas. The structural and morphological analysis describes a remarkable difference in the plasma surface interaction, nitrogen concentration, and nitrogen configurations in GNWs concerning the plasma treatment conditions. As the result of plasma treatment, the creation of structural defects and their healing upon prolonged treatment is determined with several spectroscopic and microscopic techniques. These results, along with the other measurements, revealed that the configurations of the nitrogen groups in graphene are highly influenced by the structural defects formed during the processes. Also, the electrical conductivity of the N-GNWs is strongly influenced by the concentration and different configurations of C-N bonding. These findings demonstrate the potential of plasma to tune the graphene lattice by controlled surface engineering in a fast and facile green approach, which can be fruitful for several future electronics and energy devices.
(Invited) Light-Emitting Devices Based on Defect-Enhanced Group-IV Nanostructures
Authors: Brehm Moritz
Published: July 2022

Combining Si-based integrated optics with Si-based microelectronics is crucial for next-generation applications ranging from data transfer on short distances to sensing and, potentially, to quantum cryptography at telecom wavelengths. However, Si's intrinsically poor light-emitting properties, i.e., its indirect energy bandgap, inhibit a straightforward implementation of telecom devices such as light-emitting diodes and lasers operating at room temperature.

We argue that adding Ge heterostructures, nanostructures, intentionally-induced defects, and defects within nanostructures to the Si platform can be a viable way to overcome the limitations of Si as a light-emitting material [1]. Significant progress for light-emission from group-IV nanostructures can be achieved by intentionally incorporating extended point defects inside the QDs upon in-situ low-energy ion implantation [2],[3]. This work discusses the superior light-emission properties from such defect-enhanced quantum dots (DEQDs) and our present understanding of their structural formation and light-emission mechanisms [4], indicating that optically direct recombination paths play a role in room-temperature light emission.

As compared to other group-IV systems with pronounced optical emission, contact doping and hence fabrication of electrically driven devices is relatively straightforward in this nanosystem since DEQDs are embedded into a defect-free Si matrix [5],[6]. We show that useful electrically driven devices, such as light-emitting diodes (LEDs), can be fabricated employing optically active DEQD material. These LEDs exhibit exceptional temperature stability of their light-emission properties even up to 100°C, unprecedented for purely group-IV-based optoelectronic devices [7]. We discuss the role of vital parameters, such as the temperature stability of the structural properties [8],[9], the scalability of the light-emission with the nanostructure density [6], and passivation schemes to further improve the optical properties [8],[10]. Additionally, we elaborate on schemes for advanced layouts for electrically-pumped devices.

References

[1 ] M. Brehm, Silicon Photonics IV, 67-103, Silicon Photonics IV: Innovative Frontiers, edited by David J. Lockwood and Lorenzo Pavesi, Springer series Topics in Applied Physics (2021).

[2] M. Grydlik et al., ACS Photonics 3, 298–303 (2016).

[3] M. Grydlik et al., Nano Lett. 16, 6802–6807 (2016).

[4] F. Murphy-Armando et al., Phys. Rev. B 103, 085310 (2021).

[5] M. Brehm and M. Grydlik, Nanotechnology 28, 392001 (2017).

[6] H. Groiss et al., Semicond. Sci. Technol. 32, 02LT01 (2017).

[7] P. Rauter et al., ACS Photonics 5, 431-438 (2018).

[8] L. Spindlberger et al., Crystals 10, 351 (2020).

[9] L. Spindlberger et al., Physica Status Solidi (a) 216, 1900307 (2019).

[10] L. Spindlberger et al., Appl. Phys. Lett. 118, 083104 (2021).
(Invited) Rare-Earth-Doped Tellurium Oxide Light Emitting Nanophotonic Devices
Authors: Bradley Jonathan
Published: July 2022

Tellurium oxide is a promising material for passive, nonlinear and rare-earth-doped active photonic devices because of its high transparency, high refractive index, high nonlinearity and unique structure allowing for high rare-earth solubility. In this talk I present on our recent progress on tellurite glass on-chip light emitting nanophotonic devices. Low-loss passive devices including high-Q-factor microdisks and microring resonators will be discussed. In addition, rare-earth-doped active devices, including erbium-doped and thulium-doped waveguide amplifiers and microlasers will be presented. Using similar structures, we demonstrate nonlinear light emission via four-wave-mixing, supercontinuum generation and third harmonic generation. These tellurium oxide integrated nanophotonic devices are highly promising for compact and low-cost passive, active and nonlinear photonic integrated circuits for applications in communications, computing, and sensing.
(Invited) Monolayer h-BN: Epitaxy, Properties, and Emerging Device Applications
Authors: Mi Zetian , Wang Ping , Laleyan David , Wu Yuanpeng
Published: July 2022

Hexagonal boron nitride (h-BN) has shown tremendous promise when used alongside other two-dimensional (2D) materials such as graphene, and as a wide-bandgap semiconductor for deep-ultraviolet optoelectronics and quantum photonics. Owing to its large bandgap energy comparable or higher than Al(Ga)N, h-BN can be used to form heterostructures to address some of the critical challenges of Al(Ga)N-based systems. To date, however, many fundamental material properties of h-BN remain unknown. For example, its bandgap energy remains under debate, with reports spanning from 5.9 to 6.5 eV. There is also strong controversy as to whether h-BN has a direct or indirect bandgap. In this context, We have studied the epitaxy of h-BN by using ultrahigh temperature (up to 1850 °C) plasma-assisted molecular beam epitaxy (MBE) on sapphire, Ni and HOPG substrates. We show that, when grown at sufficiently high temperature, h-BN can exhibit predominantly excitonic emission at ~220 nm. The measured luminescence intensity is orders of magnitude higher than AlN under identical conditions. By forming a p-i-n structure using this high-quality h-BN as the active region, the current-voltage (I-V) and electroluminescence characteristics of a first demonstration of a h-BN deep UV LED will be reported.
(Digital Presentation) Synthesis and Characterization of TiO2 Nanotubes for Solar Cell Applications Using an Anodizing Procedure
Authors: Karbalaei Saleh Golnaz , Rasouli Milad , Ghorannevis Zohreh , Ghoranneviss Mahmood
Published: July 2022

As the photoanode material, TiO2 is the backbone of cost-effective dye-sensitized solar cells. Herein, we propose a green, low-cost, and environmentally friendly synthesis method for titanium dioxide nanotubes using the anodizing process. The anodizing process was carried out in a chemical cell, and the effect of voltage and anodizing time on the creation of pure titanium dioxide nanotubes was investigated. A grade 4 titanium sheet with a thickness of 1 mm was utilized to make titanium oxide nanotubes. First, the titanium sheet was sliced into 1.5 × 1.5 cm squares, and the samples were sanded and polished with SiC sanding sheets ranging in grade from 180 to 3000. After that, the samples were immersed in an ultrasonic bath for 15 minutes to degrease and remove surface impurities in an equal amount of acetone-ethanol solution. A two-electrode cell was utilized for anodizing, with a graphite electrode as the cathode, a titanium sample as the anode, and an electrolyte solution containing 0.5 percent by weight of HF acid and 1:7 acetic acid with a pH of 3.5. The anode and cathode were separated by four centimeters. Different voltages and times were applied and studied in this experiment. Anodization was performed on samples produced at 20 and 15 volts for 15 and 30 minutes, respectively. The crystallization of titanium dioxide nanotubes, as well as their strength and stickiness, were caused by annealing these layers. The electrical characteristics, microstructure, and phases generated before and after heat treatment were investigated using XRD, FESEM, and FPP tests. The titanium dioxide nanotubes were then stacked using the DC sputtering method to increase their structural, crystallographic, and electrical properties for application in solar cells at three different distances of 3, 4, and 5 cm.
(Digital Presentation) Sourcing in-Operation Battery Data from Android Devices
Authors: Schimpe Michael
Published: July 2022

Battery dynamics and battery degradation are complex topics, which are typically analyzed in laboratory experiments. With controlled ambient conditions and repetitive loads, insights can be drawn for specific parameters.

In the real world, however, barely any application load is simply repetitive and ambient conditions may vary strongly. To understand real-world operation and degradation, large data sets of real-world data must be analyzed. Howey states a necessity for datasets spanning years of operation in different applications across thousands to millions of cells [1]. Such large data sets are not openly available today.

With over 2 billion Android devices in use today, and most devices equipped with a lithium-ion battery and connected to the internet, the Android devices present a potential data source for Academia. In all devices, primarily the battery current, terminal voltage, and battery temperature are collected. Secondary, on-board estimations such as State of Charge and State of Health are calculated.

This talk presents an overview of sourcing battery data from Android devices and the applicability to battery research.

References

[1] Howey, David A. "Tools for battery health diagnostics and prediction." The Electrochemical Society Interface 28.1 (2019): 55.
Low-Error Estimation of Half-Cell Thermodynamic Parameters from Whole-Cell Li-Ion Battery Experiments: Physics-Based Model Formulation, Experimental Demonstration, and an Open Software Tool
Authors: Hu Victor Waiman , Schwartz Daniel T.
Published: July 2022

Low C-rate charge and discharge experiments, plus complementary differential voltage or differential capacity analysis, are among the most common battery characterization methods. Here, we adapt the multi-species, multi-reaction (MSMR) half-cell thermodynamic model to low C-rate cycling of whole-cell Li-ion batteries. MSMR models for the anode and cathode are coupled through whole-cell charge balances and cell-cycling voltage constraint equations, forming the basis for model-based estimation of MSMR half-cell parameters from whole-cell experimental data. Emergent properties of the whole-cell, like slippage of the anode and cathode lithiation windows, are also computed as cells cycle and degrade. A sequential least-square optimization scheme is used for parameter estimation from low-C cycling data of Samsung 18650 NMC|C cells. Low-error fits of the open-circuit cell voltage (e.g., under 5 mV mean absolute error for charge or discharge curves) and differential voltage curves for fresh and aging cells are achieved. We explore the features (and limitations) of using literature reference values for the MSMR half-cell thermodynamic parameters (reducing our whole-cell formulation to a 1-degree-of-freedom fit), and demonstrate the benefits of opening up the degrees of freedom by letting the MSMR parameters be tailored to the cell under test, within constrained bounds near the half-cell reference values. Bootstrap analysis is performed on each dataset to show the robustness of our fitting to experimental noise and data sampling over the course of 600 cell cycles. The results show which specific MSMR insertion reactions are most responsible for capacity loss in each half-cell and the collective interactions that lead to whole-cell slippage and changes in useable capacity. Open-source software is made available to easily extend this model-based analysis to other labs and battery chemistries.
Design of a Scavenging Pyrrole Additive for High Voltage Lithium Ion Batteries
Authors: Liao Chen , Yang Jianzhong , Rodrigues Marco-Tulio F , Yu Zhou , Son Seoung-Bum , Liu Kewei , Dietz Rago Nancy , Cheng Lei , Zhang Zhengcheng , Abraham Daniel P.
Published: July 2022

We report 1-(dimethylamino) pyrrole (PyDMA) as an electrolyte additive for high voltage lithium ion batteries based on LiNi0.6Mn0.2Co0.2O2 (NMC622)//Graphite with an upper cutoff voltage of 4.4 V. Density Functional Theory (DFT) modeling indicates that the unique structure of PyDMA could be effective in preventing the hydrolysis of LiPF6 in a carbonate electrolyte, mitigating issues related to HF formation. The calculations also indicated that the additive would oxidize at lower potentials than typical electrolyte solvents, which could lead to protective films at the cathode surface. These expectations were tested using Nuclear Magnetic Resonance (NMR) and extensive electrochemical characterization. NMR studies confirmed the superb dehydrating capability of PyDMA, which successfully prevents HF formation even at high water content. Addition of 0.5 wt% PyDMA resulted in improved capacity retention in full-cells, and also in lower levels of transition metal dissolution from the cathode. Incremental capacity (dQ/dV) analysis indicates that benefits of PyDMA at low concentration (0.5-1 wt%) are associated with decreased rates of Li+-trapping reactions, and that higher concentrations of the additive can lead to isolation of cathode domains. Our study indicates that PyDMA could be a promising electrolyte additive for high voltage lithium ion batteries at a low concentration.
Corrosion of Ni-Coated Can Hardware of Li-Ion Batteries in Organic-Based LiPF6 Electrolytes
Authors: Stosevski Ivan , Bonakdarpour Arman , Smith Scott R. , Jacobs Allan , Way Brian , Wilkinson David P.
Published: July 2022

Water contamination of Lithium Ion Battery (LIB) electrolytes leads to hydrofluoric (HF) acid formation1, which impacts the formation2 and degradation3 of the SEI layer as well as causing corrosion of the positive electrode oxide materials and inactive components of the cell4. One of the inactive components that corrodes is the Ni-coated steel can used in the commercial 18650 cells. This paper presents for the first time a detailed report of Ni corrosion in water-contaminated organic-based LiPF6 electrolytes. The study reveals the chemical and electrochemical nature of Ni corrosion. Cyclic voltammetry, chronoamperometry and Tafel analysis coupled with electrochemical quartz microbalance (EQCM) technique were used to investigate the mechanism of the Ni dissolution at OCV and near OCV potentials (2.5 V – 3.5 V vs. Li/Li+). Chronoamperometry at a potential close to OCV gives a current and mass plateau for the first few hours (4 – 6 h) followed by a sudden oxidation current and mass loss due to Ni dissolution (Figure 1) indicating the generation of electrolyte-soluble corrosive species, which was confirmed by testing a pristine Ni electrode in the same used electrolyte (Figure 1). Speciation of dissolved Ni and generated corrosive species is of the great importance for revealing the mechanism and is in the focus of the ongoing research. SEM reveals pitting corrosion of Ni in LiPF6 based electrolytes.

References

M. Stich, M. Göttlinger, M. Kurniawan, U. Schmidt, and A. Bund, J. Phys. Chem. C, 122, 8836–8842 (2018).

D. Strmcnik et al., Nat. Catal., 1, 255–262 (2018).

J. G. Han et al., J. Power Sources, 446, 227366 (2020).

L. Yang, M. Takahashi, and B. Wang, Electrochim. Acta, 51, 3228–3234 (2006).

Figure 1. Three-electrode EQCM: Ni electrode mass change in 0.25 % water spiked 1 M LiPF6/EC/DEC (1:1) electrolyte during chronoamperometry at 3.35 V vs. Li/Li+.

Figure 1
Electrolyte Design for Anode-Free Lithium Metal Batteries
Authors: Zhou Chengtian , Thangadurai Venkataraman
Published: July 2022

Current lithium-ion batteries (LIBs) are approaching their energy density limits and thus may not keep up with the ever-increasing demand for higher specific energy density in today’s energy storage and power applications. Anode-free lithium metal batteries (AFLMBs) utilize the full theoretical capacity of Li metal anode (3860 mAh g-1, ten times higher than lithiated graphite) and offer lower cost and better safety than cells with Li excess. However, due to the low efficiency of Li deposition and stripping, AFLMBs suffer from rapid capacity loss.

In this presentation, we will discuss a unique coin cell configuration design with high compression for AFLMBs. The high pressure leads to more stable cycling performance, providing a more accurate assessment of AFLMBs.1 A carbonate-glyme hybrid electrolyte for AFLMB is demonstrated with a capacity retention of 73% for 50 cycles. The hybrid electrolyte possesses a unique solvation structure, where diglyme solvates both Li-ions and film-forming additive, while carbonates dilute the mixture, enabling facile ion migrations.2

C. Zhou, A. J. Samson, M. A. Garakani, and V. Thangadurai, J. Electrochem. Soc., 168, 060532 (2021).

C. Zhou et al., Energy Storage Mater., 42, 295–306 (2021) https://doi.org/10.1016/j.ensm.2021.07.043.
(Invited) Investigations into the Role of Adsorption Processes in Alloy Deposition
Authors: Moffat Thomas P , Liu Yihua , Gokcen Dincer , Ou Yang Liang Yueh , Hwang Sun Mi , Hangarter Carlos M , Ambrozik Stephen , Dimitrov Nikolay , Bertocci Ugo
Published: July 2022

The interplay between adsorption, underpotential deposition and excess bond enthalpy in the deposition of alloys and intermetallic will be discussed based on selections from recent work. Examples of limiting behavior will be presented that range from the deposition of solid-solutions, e.g. Pt-Cu and Pt-Fe group alloys, to intermetallics, e.g. Pt-Pb, to immiscible, e.g. Cu-Pb, systems. In addition, the impact of “parasitic” reactions, such as electrolyte breakdown, on the deposition of elements and alloys will be briefly discussed. The utility of a close coupling between electroanalytical, gravimetric, metallurgical and surface science measurements to reveal the underlying thermodynamic and kinetic influences on co-deposition process will be highlighted.
Cu2(ZnSn)(S)4 Electrodeposition from a Single Bath By Both DC and Pulsing Current with Atomic Ratio Optimization
Authors: Saeed Mahfouz
Published: July 2022

Cu2(ZnSn)(Se)4 (CTZSS) has an significant advantages over CIGS as thin film solar cell due to its optimum band gap. Producing thin film layers by electroplating techniques is chiefly attractive due to low production cost and high throughput 1-3. Several publication reports CTZS electrodeposition; however, the electrodeposition method still has an important challenge such as a annealing process due to partial pressure variation4.

We introduce in this work an advance lower electrolyte concentration which suitable to single bath electroplating similar to prvious work with CIGS5. The electrolyte is significantly more dilute in comparison to common electrolytes designated in the literature1-4. We use pulsing technique with current pulsing technique to improve the deposit adhesion and quality. Theelectrolyte composition is: 0.0042 M CuSO4, 0.0031 M ZnSO4, 0.0051 M SnCl2, 0.0062 M Na2S2O3, and 0.19 mM Na2S2O3. PHydrion is used as a buffer (pH=2), and 0.61 M LiCl is used as supporting electrolyte.

Electroplating experiments was carried out at a rotating disk electrode system which provides a better controlled electroplating condition. Rotating disk function is to have better control to experiment parameters and to compare Dc current efficiency with pulsing current. electrochemical behavior study and the deposit equality investigation are provided in Fig. 1. The effects of pulsing time and current density on the CTZS alloy atomic composition, deposit quality, and its adhesion to the back contact are discussed. The post annealing treatment was performed under sulfur element atmosphere with no necessity for metals addition at this phase. The electroplating parameters was optimized according. The final composition was investigated using Energy-dispersive X-ray spectroscopy technique (EDS) Fig. 2. XRD technique used to analyze CTZS crystallography and thickness.

Acknowledgements

Case Western Reserve University for using their instruments

References

[1] M. Cao, L. Li, B. L. Zhang, J. Huang, L. J. Wang, Y. Shen, Y. Sun, J. C. Jiang, G. J. Hu,

Sol. Energy Mater. Sol.Cells, 93, 583 (2009).

[2] Y. Lin, S. Ikeda, W. Septina, Y. Kawasaki, T. Harada, M. Matsumura, Sol. Energy Mater. Sol. Cells, 120,

218 (2014).

[3] H. Guan, H. Shen, C. Gao, X. He, , J. Mater. Sci.:Mater. Electron., 24, 1490 (2013).

[4] S. Abermann, , Solar Energy, 94, 37 (2013).

[5] Saeed, M.; González Peña, O.I, Nanomaterials 2021, 11,

Figure 1
Chemical Analysis of High Energy Density Electrodeposited Silicon Anodes for Lithium-Ion Batteries
Authors: Fritz Nathan Joseph , Jeong Hyewon , Zahiri Beniamin , Sun Pengcheng , Caple Michael , Yang Zhenzhen , Ma Jingcheng , Cahill David G. , Braun Paul V.
Published: July 2022

Implementation of high Si-content anodes (> 10% v/v%) has been difficult to achieve at the loadings and manufacturing scale required for practical lithium-ion batteries (LIBs) applications. Three-dimensionally engineered electrically conductive porous scaffolds enable low silicon coating thicknesses (10-200 nm) and provide internal free volume to reduce the impact of Si volume changes upon cycling. Yet, scalable deposition of battery-grade silicon on these complex structures remains a challenge. Herein, we report a high energy-density Si-dominant electrodeposited material (EDEP-Si) onto 3D-structured Ni scaffolds and evaluate the impact of impurities inherent to the electrodeposition process on performance by comparing the behavior of the EDEP-Si with that of high-purity amorphous Si grown via static chemical vapor deposition (CVD). The long-term cycling stability and high reversible specific capacity of EDEP-Si and CVD-Si on a silicon basis are remarkably similar and near theoretical (~2400 mAh g-1 Si-1 after 100 cycles). However, the EDEP-Si exhibits a 13% lower first cycle efficiency and reduced round-trip efficiencies over the first 10-20 cycles relative to CVD-Si. Reactions between carbon (9-11 at%) and, more importantly, oxygen (42-44 at%) in the EDEP-Si with lithium are most likely responsible for the reduced early-cycle round trip efficiencies and low capacity relative to the mass of the total deposit. Based on our observations, we suggest directions for improving the composition and properties of EDEP-Si.
(Digital Presentation) Electroless Deposition of Oxidation Resistant High-Temperature Silicide Coatings on Molybdenum and Tzm Alloy Using Molten Salt
Authors: Göynük Tansu , Ömür İshak Emre , Erdogan Metehan , Karakaya Ishak
Published: July 2022

Molybdenum is one of the refractory metals which has high melting point, 2620oC, and good mechanical properties. Unfortunately, oxidation resistance of molybdenum is not satisfactory for certain applications which involves high temperatures; therefore, an oxidation resistant coating is necessary. Molybdenum di-silicide (MoSi2) was coated on pure molybdenum and TZM alloy to increase oxidation resistance at high temperatures by electroless molten salt method. A molten salt solution containing NaCl, KCl and NaF was used to apply coating at temperatures above 600oC. Silicon powder and Na2SiF6 were used as silicon source during coating process. Experiments were carried out at different temperatures, durations and salt compositions. Coating thickness, surface roughness, resulting phases and coating behavior of pure molybdenum and TZM alloy were evaluated. X-ray diffraction (XRD), Inductively Coupled Plasma – Mass Spectrometer (ICP-MS) and scanning electron microscope (SEM) were conducted in characterization of the silicide coatings.
(Digital Presentation) Electronic and Optical GAP Evaluation By Oxygen Tuning in MOSE2
Authors: Amini Moharam , Torabi Kamran , Jamilpanah Loghman , Mohseni Seyed Majid
Published: July 2022

In this study, a simple and fast electrochemical method was employed to synthesis molybdenum diselenide thin film. Molybdenum diselenide films have been electrodeposited on FTO substrates from an ammoniacal solution of H2MoO4 and SeO2. We fabricated thin films composed of MoSe2, MoO2 and MoO3 elements by adjusting some electrodeposition factors, e.g., deposition time and potential. The Structural characterizations of the electrodeposited films were investigated by SEM, Scanning tunneling spectroscopy (STS), Raman spectroscopy and UV-Visible spectroscopy. And also, Electronic and optical gap have been measured by STS and UV-Vis spectra, respectively.
Tuning Ionic Conductivity and Stability of Li10GeP2S12 Solid-State Electrolyte
Authors: Isarraras Gustavo , Dang Tung , Mashaleh Dirar , Oye Michael , Oh Dahyun , KC Santosh
Published: July 2022

All-solid-state Li-ion batteries gained a huge attention because they exhibit higher power density, wider electrochemical stability windows, and overall safety of solid-state electrolytes (SSE) compared to conventional liquid electrolyte-based batteries. Unfortunately, most of the SSE materials have not matched the ionic conductivity of their liquid counterpart. But, recent research and the synthesis of new materials have shown SSE can conduct ions at an equivalent or even higher rate. However, the electrochemical stability needs to be improved. There is a growing research effort in identifying a solid electrolyte that is both electrochemically stable and has a very high ionic conductivity. The Li10GeP2S12 (LGPS) is one of the superionic conductors, is known for its high ionic conductivity that can be deployed as a solid electrolyte in batteries. However, LGPS is not stable as exposed to air and moisture, posing challenges during its manufacturing, and designing process. Thus, in an attempt to optimize the stability and ionic conductivity, the effect of antimony (Sb), tin (Sn), and oxygen (O) substitution on conductivity and stability of LGPS is investigated using Density Functional Theory (DFT). The systematic study of compositional variation, phase stability, defects chemistry, and the impact on electronic properties and ionic conductivity is performed. Thus, this study will provide significant insights on ion conduction mechanisms and strategies that can tune the ionic conductivity and stability of LGPS based electrolytes.

This project was supported in part by COE SJSU, DOE NERSC, and XSEDE.
(Digital Presentation) Free Solvent Molecules in the Electrolyte Leading to Severe Safety Concern of Ni-Rich Li-Ion Batteries
Authors: Joraleechanchai Nattanon , Sawangphruk Montree
Published: July 2022

The safety of Li-ion batteries is one of the most important factors, if not the most, determining their practical applications. We have found that free carbonate-based solvent molecules in the hybrid electrolyte system can cause severe safety concerns. The 18650 battery cells using the 50% varied-alkyl chain piperidinium-based TFSI result in an immediate and aggressive explosion after applying the impact test (UN38.3) compared with the cell using the conventional electrolyte, having a mild explosion after applying the impact force with 16 s-delayed time. Furthermore, the greater concentration of gases especially C2H4 and CO in the hybrid electrolyte system compared with the conventional electrolyte system was observed by online in situ DEMS, which is evidence for the aggressive explosion of the cell using the hybrid electrolyte. In additionally, the classical MD investigation is suggested that hybrid electrolytes have a high AGG concentration of Li+ and TFSI−, producing a high concentration of the isolated EC or free solvent, which could generate more gases in the fully charged battery cell. Mixing ionic liquids with a carbonate-based solvent as the co-solvent at a fixed salt concentration of 1 M LiPF6 can lead to free carbonate-based molecules causing poor charge storage performance and safety concerns.

Keywords: Ni-rich Li-ion bateriesIonic liquids; Safety; Battery explosion; Mismatch electronic properties; 1865 cylindrical cells
Reduction of a Lithium-Ion Solid Electrolyte Model Under Potentiostatic Hold
Authors: Keane Laura , Moyles Iain
Published: July 2022

Solid state electrolytes are becomingly increasingly attractive due to their improved safety, lower self-discharge, and higher power densities over the more commonly used liquid electrolyte [1,2]. Solid electrolytes are a relatively new material in the field of lithium-ion batteries, therefore there is considerably less mathematical investigation and analysis into these materials, compared with their liquid counterparts.

We review a model for a solid electrolyte from thermodynamics principles [3]. We non-dimensionalise and scale the model to identify small parameters, where we identify a scaling that widens the boundary layer in the electrolyte compared to previous literature. We consider an Li2O solid electrolyte which is attached on each end by blocks of solid lithium. We fix a potential difference across the electrolyte and consider different charge flux conditions. We present asymptotic analysis and numerical solutions for both the zero-charge flux equilibrium and for the non-zero charge flux equilibrium problems. We consider numerical simulations of the full-time dependent problem and show that there are two important time scales in the problem, an early transient timescale where the boundary layers first approach their equilibrium followed by a longer timescale where we observe the transience in the bulk of the solution.

We briefly talk about the application of a solid electrolyte to cylindrical nanowire electrodes. Recent advances in electrode chemistry have allowed for cylindrical nanowire geometries exhibiting low-capacity fade. However, the performance of these electrodes is very sensitive to experimental conditions and early charge behavior and thus it is important to understand the lithium transport process in these systems. Following from this work, we will combine the solid electrolyte model with a nanowire electrode in order to investigate these processes.

References

[1] A. Manthiram, X. Yu, Xingwen, and S. Wang. Lithium battery chemistries enabled by solid-state electrolytes, Nature Reviews Materials, Nature Publishing Group, 2(4), 1-16, 2017.

[2] Z. Chen, G. Kim, Z. Wang, D. Bresser, B. Qin, D. Geiger, U. Kaiser, X. Wang, Z.X. Shen, and S. Passerini.

4-V flexible all-solid-state lithium polymer batteries, Nano Energy, Elsevier, 64, 103986, 2019.

[3] S. Braun, C. Yada, and A. Latz. Thermodynamically consistent model for space-charge-layer formation in a solid electrolyte, The Journal of Physical Chemistry C, 119(39), 22281-22288, 2015.
Laser-Structured Electrodes for Lithium-Ion-Batteries – Dependence of Structure Density on Fast Charging Capability
Authors: Kouli Maher , Kouli Maher , Dilger Klaus
Published: July 2022

The significant increase in energy density is a declared development goal for lithium-ion batteries for applications in electric vehicles. This implies the use of electrodes with significantly increased areal capacity and mass loading. It is known from a large number of investigations that with increasing electrode thickness both lithium ion diffusion in the electrolyte and electron transport to the current collector dominate, leading to insufficient current carrying capacity electrodes. To achieve an improvement of the fast charging capability of high areal capacity electrodes, they are getting structured, which maximizes the surface area between the electrolyte and the electrode. By means of structuring, electrodes with a high areal capacity can achieve both a high specific discharge capacity and a sufficient fast charging capability. The aim of the perforation is to minimize the resistances and to generate an increased surface area between the electrolyte and the electrode, which leads to new transport paths for the lithium ions. Previous publications show that the laser-structuring of anodes and cathodes lead in particular to an improvement of the charge/discharge rates and cycle stability [Habedank 2018/2019, Kraft 2019, Smyrek 2019].

Recent findings indicate there is a relationship between structure density and electrochemical (fast charge/discharge capability) properties. The goal of the presented work is, to determine the dependence of structure density on fast charging capability. For this purpose, anodes and cathodes are symmetrically processed with different spot density, from which full cells are built and analyzed after electrochemical tests. Graphite-silicon anodes with an area capacity of 8,0 mAh/cm² and cathodes with an area capacity of 6,0 mAh/cm² will be processed with spot distances from 180 µm to 510 µm.
Metal Nitrate Embedded Polymeric Interlayer for Improving Cycling Stability of Li Metal Anode
Authors: Shin GeunHyeong , Cho EunAe , Kang Hyeonmuk , Kim Taehee , Hwang GyuSeong , Lee Junho
Published: July 2022

Among secondary batteries using lithium, the use of lithium metal anodes for high capacity has become a hot topic. However, in lithium metal anodes, there is a major problem of dendritic growth and research are actively underway to address the issue. And it is reported that it is possible to improve the stability of Li metal anode by facilitating the movement of lithium ions through various additives to suppress dendritic growth and to make robust and stable SEI layer. To address the issue of dendritic growth of Li, using cesium nitrate is selected to improve the stability of the anode based on a mechanism by which a nitrogen-rich compounds lithiophilic to transport Li ion uniformly are formed in the SEI layer. And also the cesium element induces an cation electrostatic shielding effect while lithium metal is deposited and grown in the anode. In addition, since metal nitrates have very low solubility in carbonate-based electrolytes, polymer nanofiber-interlayer is synthesized by electrospinning to support metal nitrate and supply nitrate continuously and stably, while interlayer does not interfere with the movement of lithium ions through the nanofiber layer.

In summary, a metal nitrate embedded polymer nanofiber layer is synthesized through an electrospinning method, then stabilization of a lithium surface and stability of a lithium metal anode are obtained by using an intermediate layer, and a relationship between an additive and SEI formation is identified at a limited solubility in carbonate electrolytes. The study result demonstrates that the lifetime of symmetric Li-Li cells and full cell with LCO cathodes improved greatly. And the deposition morphology of Li become dendrite-free and more uniform.
(Digital Presentation) Straightforward Combustion Synthesis of Tin/Carbon Composite As Anode for Lithium-Ion Battery with Long Cycle Life
Authors: Vashishth Surishi , Singh Dheeraj , Prabhakaran Vinod C. , Eswaramoorthy Muthusamy
Published: July 2022

The theoretical specific capacities of alloy-based anodes such as Si, Ge, P, Sn, Sb are 2–10 times higher than that of graphite. Tin-based anode materials gained prominence in battery applications owing to their high theoretical capacity, less toxicity, and low cost. However, they suffer from huge capacity losses due to severe volumetric expansion up to 300%. Here in our poster, Sn@C (20 wt% Sn) composite synthesized by single-step combustion process showed good adherence of tin particles on graphite rich carbon which successfully minimizes pulverization with enhanced structural stability. The homogeneously dispersed tin nanoparticles exhibit a highly reversible capacity of 281 mA h g−1 at 300 mA g−1 with 98.6% capacity retention after 300 cycles and 94.6% capacity retention at 500 mA g−1, after 700 cycles. After cycling, ex-situ XRD and TEM images showed Sn@C intact due to intimate interaction as in Sn-O-C linkage.

Figure 1
(Digital Presentation) Earth-Abundant Copper-Based Electrode Materials for Li-Ion Storage
Authors: Tripathy Debashis , Sampath S
Published: July 2022

Lithium-ion batteries (LIBs) find their use in almost all applications starting from electronic gadgets to grid energy storage and hybrid electric vehicles. In this direction, the development of high-capacity anodes is crucial to fulfil the increasing energy demand. To evaluate the Li+ ion storage performance, we have synthesized an earth-abundant copper-based electrode material, Cu3PS4, using the chemical vapor transport (CVT) method from the constituent elements Cu, P, and S in a 3:1:4 ratio. It has an enargite-type structure and has a layered-type morphology (Figure 1a). A high capacity of 970 mAh g-1 is obtained at 0.1 A g-1 current density. The electrode is amenable for high discharge rates up to 5 A g-1, and at a discharge rate of 1 A g-1, the cell can be cycled 5000 times with 90% capacity retention. The high electrochemical performance of the material is related to the conversion reaction as probed by in situ Raman spectroscopy (Figure 1b) and surface-controlled capacitive contribution due to the formation of a polymeric film over the electrode surface. A full cell with LiCoO2 cathode results in a large number of cycles with stable performance. Further improvement is achieved by forming a composite with an organic polymer, polybenzimidazole. The composite electrode delivers almost double the capacity of the pristine electrode. Other studies on the use of the electrode material to multivalent ion storage based on Mg2+, Zn2+, and Al3+ are in progress.

Reference

D. Tripathy and S. Sampath, J. Power Sources 2020, 478, 229066.

Figure 1. (a) Unit cell structure and SEM image of Cu3PS4 and (b) in situ Raman spectra of the electrode after discharge.

Figure 1
(Digital Presentation) Understanding the Impact of Process Conditions on Manufacturing Thick Cathodes By Systematically Reducing Inactive Material Percentages
Authors: Koggala Wellalage Dilni Kaveendi , Battaglia Vincent , Higa Kenneth , Fu Yanbao , Zhang Buyi
Published: July 2022

With the lithium-ion battery industry moving to high energy density anode materials such as silicon and lithium metal as a substitute for lower specific capacity carbon-based materials like graphite, cathode energy density can become a bottleneck. Typical cathodes have less than 10% practical specific capacity compared to both pure lithium metal and silicon. For these anodes, cathodes with higher active material loadings per unit area would be needed to produce matching electrode pairs. However, cathode thickness cannot indefinitely be increased, as doing so leads to issues with electrolyte transportation, conductivity, and mechanical properties [1,2].

Increasing the loading of the cathode could also be done by reducing the amounts of inactive components, such as the binder and the conductive additive, in the electrode. To achieve this, understanding the role of each component is important. The most important role of the binder is to act as an adhesive among particles and the current collector. But most binders are electronically insulating. The main role of the conductive additive, such as carbon black, is to improve the conductivity of the overall system [1].

As the inactive material percentages are decreased, the distribution of these components in the electrode domain becomes more important to both the electrochemical and mechanical performance of the electrode. The distribution changes with the different process conditions used, such as mixing techniques, order, speeds, times, slurry viscosity, drying conditions, etc. This research consists of a systematic study to understand the effects of the aforementioned process conditions on the particle and polymer distribution as well as its contribution to the mechanical and electrochemical performance. With the use of the current findings, the active material percentage was increased up to 98% in electrodes with 5 mAh/cm2 loading, retaining similar performance to electrodes with 92.8% active material, as shown in figure 1. Some contribution of the capacity fade was found to be due to the lithium counter electrode used.

The goal of this ongoing project is to produce a model that could be applied to different materials to identify the best process conditions for thick electrode manufacturing.

References

F. Ma, Y. Fu, V. Battaglia, R. Prasher, Microrheological modeling of lithium-ion battery anode slurry, J. Power Sources, 438 (2019), p. 226994

Wen Yu, Nanping Deng, Lin Tang, Kewei Cheng, Bowen Cheng, Weimin Kang, Roles of metal element substitutions from the bimetallic solid-state electrolytes in lithium batteries, Particuology, 65 (2022), p. 51-71

Figure 1