bluuebunny/crossref_metadata_2025 huggingface dataset:
(Invited) Combining Machine Learning, DFT, EFM, and Modeling to Design Nanodielectric Behavior
Authors: Schadler Linda S , Chen Wei , Brinson L. Catherine , Sundararaman Ravishankar , Prabhune Prajakta , Iyer Akshay
Published: July 2022

Polymer Nanodielectrics are class of materials with intriguing combinations of properties. Predicting and designing the properties, however, is complex due to the number of parameters controlling the properties. This makes it difficult to compare results across groups, validate models, and develop a design methodology. This presentation will share a recent approach to developing a data driven design methodology grounded in physics-based models and experimental calibration. We combine finite element modeling of dielectric constant and loss functions with a Monte Carlo multi-scale simulation of carrier hopping to predict break down strength. Filler dispersion, filler geometry, isotropy and interface properties are explicitly taken into to account to compute objective functions for ideal nanodielectric insulators. Further, we have used machine learning to develop an EFM technique for directly measuring the dielectric constant of the nanoscale interfacial region as critical input to our models. Ultimately, we calculate the Pareto frontier with respect to nanocomposite constitute properties and geometry to optimize properties.

The finite element approach can be used to forward predict properties based on the properties of the interfacial region and filler dispersion, or as an inverse tool to calculate interface properties or develop optimized filler morphologies. The breakdown strength model critically depends on the energy distribution of trap states that inhibit space charge motion. We have developed an ab initio approach to determine the trap states at amorphous interfaces, and have used that to do a systematic analyses of trap distributions in composites with functionalized particle interfaces. The models all use 3D particle distributions based on 2D imaging (TEM) of the composites and publicly available tools for binarization and characterization of filler morphology. Finally, we use a design of experiment approach (Latin Hybercube Design) to sample the complete experimental design space, and using calibrated models and morphologies, create a data set spanning the full set of parameters. We use the data from the DOE to train a Gaussian Process metamodel and a genetic algorithm to determine which designs fulfill the design parameters. The talk will present several case studies as examples.

The data for this work was accessed from a new data resource, MaterialsMine, using FAIR (Findable, Accessible, Interoperable, and Reusable) principles. MaterialsMine is an open source data repository, and resource. It includes unique visualization tools as well as modeling and characterization resources.
(Invited) Size Controlled Silicon Quantum Dots: Understanding Basic Properties and Electronic Applications
Authors: Yazicioglu Deniz , Gutsch Sebastian , Zacharias Margit
Published: July 2022

The fabrication of SiOx/SiO2 superlattices combined with thermal annealing enables the size and density control of Si quantum dots. The layered-arranged Si quantum dots represent a model system to systematically study the photonic and electronic properties of indirect gap quantum dots prepared in a CMOS compatible way. Hence, the model system is used to understand the interplay of absorption and recombination, the carrier kinetics and the electronic transport properties for matrix embedded Si quantum dots. The interplay of radiative and non-radiative recombination will be discussed for high quantum yield. Doping of Si quantum dots and the respective quantification is at the limit of the respective high resolution techniques but clearly show the effect of self-purification. The effect of an externally applied electric field on exciton separation and carrier transport will be discussed..
(Invited) Optical Tweezers to Isolate Single Er Ion Emitter Containing Nanocrystals and in-Situ Perovskite Quantum Dot Analysis
Authors: Gordon Reuven
Published: July 2022

We have used optical tweezers with shaped apertures in metal films to hold onto individual nanoparticles including erbium containing nanoparticles and perovskite quantum dots. In this talk, I will talk about our ability to isolate nanocrystals with just one erbium emitter, paving the way for single photon sources at low loss fiber wavelengths. I will also talk about our new work on in-situ characterization and assembly of perovskite quantum dots, allowing to relate size to emission wavelength and look at quantum hybridization.
(Invited) Persistently Luminescent Nanoscale Materials
Authors: Fanchini Giovanni
Published: July 2022

Although alkaly earth aluminates (such as SrAl2O4 doped with Europium and Dysprosium) have been investigated as persistently luminescent (PL) materials for several decades, multiple questions still remain unanswered about their nanoscale optoelectronic properties, microscopic characterization, and their utilization in specific devices, such as, for example, after-glowing solar cells. In this talk, I will review what the scientific community, and my group, have been learning on SrAl2O4(:Eu:Dy) using nano-optical characterization tools, including scanning near field optical microscopy (SNOM) luminescence imaging to inform device fabrication. Specifically, I will review phase phase-modulated scanning near-field optical luminescence (PM-SNOL) imaging as new method for assessing the exciton diffusion length (LD) in nanoscale PL materials. Using PL we have determined that LD
is of the order of 100 μm in SrAl2O4(:Eu:Dy), a surprisingly large value, that should enable exciton storage and transfer from SrAl2O4(:Eu:Dy) micro- and nano-crystals, as opposed to simple exciton recombination with photon re-emission. With this result in mind, in the second part of our talk, we will we introduce a new family of photovoltaics capable of generating power in the dark for several hours after illumination, thanks to the afterglow redox properties of strontium aluminate codoped with Eu2+ and Dy3+ [SrAl2O4(Eu,Dy)], a persistently luminescent material incorporated at the interface between the transparent anode and the active layer of dye-sensitized solar cells (DSSC). After 9-hr operation in the dark, our photovoltaics still produce dark short-circuit currents about 75% of the current generated immediately after illumination. Control DSSCs with identical architecture, but without SrAl2O4(Eu,Dy), do not exhibit any significant generation of power in the dark. Differently from previous unsuccesful attempts to design nighttime solar cells seeking use of the reabsorption of photons persistently emitted by SrAl2O4(Eu,Dy) in relatively inefficient processes, our devices rely on the more efficient integration of Eu2+/Eu3+ and Dy3+/Dy2+ redox processes of SrAl2O4(Eu,Dy) into the electrochemistry of DSSCs, with the suppression of persistent luminescence, the direct oxidation of the iodine electrolyte by Eu3+,and the reduction of the DSSC anode by Dy2+. With the discovery of charge transfer and redox processes between strontium aluminate, titania and iodine electrolytes, our work also offers unique advances in the photo-physics of PL materials at the nanoscale.
(Invited) Nanocrystalline Oxide-Based Luminescent Nanophotonic Structures
Authors: Serna Rosalia , Gonzalo Jose , Mariscal-Jimenez Antonio , Gomez Rodriguez Pilar , Caño Andres
Published: July 2022

Light nanoemiters are the cornerstone of photonic integrated applications including displays for consumer products such as phones and smartwatches, and for advanced application such as quantum emitters. In this context it is appealing to have access to a single material platform suitable for tunable wavelength emission, and if possible, that can provide broadband white light emission. Solid state light emitting nanostructures based on Europium ions are a promising solution. When imbedded in a solid they can have two oxidation states Eu3+ or Eu2+ which upon excitation show a either a high purity red emission (associated to the Eu3+ dipole-forbidden intra-4f shell 5D0® 7F2 transition), or a broad emission band in the 450-600 nm spectral region (related to the Eu2+ dipole-allowed 4f6 5d -> 4f7 transitions). Here I will discuss the strategy that our group is following based on europium oxides EuOx, 1/3<x<1, as this approach allows to have a high density of emitters. Moreover, their electric and optical properties can be tuned from the sesquioxide Eu2O3 that is a wide bandgap dielectric that shows the Eu3+ ion related narrow band red emission, to the monoxide EuO that is a semiconductor that shows a wide band white light emission related to the Eu2+ ion. For the nanoemitters we have prepared EuOx nanocrystalline films with high transparency, and in which the coexistence of both oxidation Eu states enables wavelength tunability [1.2]. Finally, recently we have designed 2D hybrid nanoemitters by integrating the EuOx films with metallic metasurfaces in order to induce an enhancement of the emission intensity by selective plasmonic excitation [3].

[1] A. Mariscal, A. Quesada, A. Tarazaga Martín-Luengo, Miguel A. García, A. Bonanni, J.F. Fernández and R. Serna, Appl. Surf. Science 456,980 (2018).

[2] A. Mariscal-Jiménez, A. Tarazaga Martín-Luengo, B. Galiana, C. Ballesteros, A. Bonanni, J. Martín-Sánchez, R. Serna, J. Phys. Chem. C. 124, 15434–15439 (2020).

[3] P. Gomez-Rodriguez, E. Soria, Y. Jin, A. Caño, I. Llorente, A. Cuadrado, A. Mariscal-Jiménez, A. K. Petford-Long, R. Serna and J. Gonzalo, Nanophotonics. 10, 3995–4007 (2021).
(Invited, Digital Presentation) Quantum Dots Based Transparent Light Emitting Diodes
Authors: Chrzanowski Maciej , Witczak Łukasz , Podhorodecki Artur
Published: July 2022

Colloidal quantum-dot light-emitting diodes (QLEDs) have attracted considerable attention in the optoelectronic industry due to their

remarkable performance, which makes them promising candidates for displays and lightning technology with a particular emphasis on color purity, brightness, and emission tunability. For these reasons over last few years a very impressive progress has been obtained in this research area in terms of improvement of QLED external quantum efficiency, their brightness and lifetime.

While the race to improve the parameters of key importance for the operation of the QLED continues and QLEDs will be probably commercially available soon, the other topics related with QLED devices are at much less advanced level. This includes for example development of flexible, transparent or printable QLED devices or preparation of QLED devices in air.

In this paper we will present our results related with flexible and/or transparent QLED devices obtained from green Cd-based quantum dots. We will discuss optical and electrical properties of QLED devices when using as transparent, conductive electrodes PMA/Ag, MoOx/Au/MoOx or silver metal-mesh fabricated by Ultra Precise Deposition (UPD). We will also describe thin-film deposition methods such as spin-coating/sputtering or inkjet-printing as a new versatile approach towards fabrication of flexible transparent electronics.
Study of Etch Stop Layer on Characteristics of Amorphous Aluminum Oxide Thin Film
Authors: Lee Sangwoo , Lee Joonbong , Yang Jaeyoung , Choi Taekjib
Published: July 2022

To protect the active layer, which are inter layer dielectrics (ILD) and metal lines, from being damaged by UV laser during the etching process, etch stop layers (ESL) are used in patterning process of the integrated circuits (ICs) fabrication in back end of line (BEOL). The ESL material should have a higher etch selectivity than the active layer. Therefore, it must have a low dielectric constant and high chemical resistance. Aluminum oxide compounds (AlOx, AlOC, AlON, etc.) are highly suitable for use as ESL due to the low dielectric constant between about 4 and 9, high etch selectivity, high density (2.5-3.8 g/cm3) and pattern transfer capability. We focused on lowering the dielectric permittivity and increasing the density by controlling the precursor/reactant pulsed time of atomic layer deposition (ALD).
Investigation of Garnet Solid Electrolyte-Layered Oxide Cathode Interfaces Towards Cylindrical High-Performance Li-Ion Batteries
Authors: Bunyanidhi Panyawee , Sawangphruk Montree
Published: July 2022

Even though the Ni-rich cathode materials (Ni content > 60%), providing high energy density and high capacity, can draw much attention for advanced lithium-ion battery (LIB) community and industry, several drawbacks such as poor structural stability, thermal stability, and capacity fading still restrict their scalable application. Herein, the trace amount of garnet Li7La3Zr2O12 (LLZO) oxide solid-state electrolyte was introduced on the LiNi0.8Mn
0.1
Co0.1O2 (NMC811) cathode as a scaffolding interfacial layer on NMC particles via a one-step solvent-free mechanofusion process. The interfacial La-Ni exchange after mechanofusion was investigated by the extended X-ray absorption fine structure (EXAFS) measurement. Subsequently, the in situ X-ray diffraction was used to investigate the crystallographic evolution during the charge-discharge process. The NMC-LLZO cathode exhibits excellent rate capability and cycling performance, especially at high current density. The LLZO interfacial layer was found to be able to delay Li insertion into NMC bulk which in turn led to a better Li distribution and higher rate capability over pristine NMC. The practical applications of NMC-LLZO are also presented in 2.5 Ah 18650-format lithium-ion batteries. The cells can perform from C/10 to 1C with only 16% capacity reduction and remain 80% retention after cycled up to 500 cycles at a high current density of 1C compared to 40% of NMC cells.

Keywords: LiNi0.8Mn0.1Co0.1O2, Lithium-ion batteries, Oxide solid-state electrolyte, Scaffolding layer, High current density
Adapting Simultaneous in Operando Electrochemical Quartz Crystal Microbalance (EQCM) and Electrochemical Impedance Spectroscopy (EIS) to Studies of SEI Layer Formation on Amorphous Silicon Anodes
Authors: Morris Louis Vincent , Ortiz-Ledon Cesar , Hamers Robert J
Published: July 2022

Lithium-ion Batteries (LIBs) are the electrochemical energy storage technology of choice for an incredible range of technologies, from handheld consumer electronics to electric vehicles. Since their introduction, the application of these batteries has been limited by their energy density, which is in turn currently gated by the low theoretical energy density of the graphite anodes that are standard in the field. Si has long been targeted as a next generation anode material, with a theoretical energy density almost 10 times larger than graphite, however uncontrolled electrolyte decomposition on its surface has caused poor cycle life and low columbic efficiencies in Si-containing cells1. In this work, a new class of organosilicon (OS) additives were introduced to the Si anode literature and their effect on the first-cycle electrochemistry on model anode surface was explored using in operando electrochemical quartz crystal microbalancing (EQCM) and electrochemical impedance spectroscopy (EIS). Ex situ x-ray photoemission spectroscopy (XPS) was also used to investigate the differences in chemical composition of solid electrolyte interface (SEI) layers formed in the presence and absence of additive. EQCM-EIS experiments demonstrated an increase in cell impedance early in the cycle, which lead to the suppression of early electrolyte decomposition on the model anode surface. Subsequently, lithiation and delithiation proceeded more efficiently and with lower impedance in additive-treated cells. Finally, XPS investigations of the SEI composition revealed that OS-treated cells create thinner SEI layers that were richer in LiF and contained less organic material than cells without OS.

(1) Jin, Y.; Zhu, B.; Lu, Z.; Liu, N.; Zhu, J. Challenges and Recent Progress in the Development of Si Anodes for Lithium-Ion Battery. Adv. Energy Mater.
2017, 1700715, 1–17. https://doi.org/10.1002/aenm.201700715.
(Digital Presentation) Numerical Characterization of Physical Properties of Microstructures in Lithium-Ion Batteries
Authors: Balasubramanian Ganapathi RAMAN , Salazar-Tio Rafael , Sun Zhuang , Crouse Bernd , Oancea Victor
Published: July 2022

In this paper, we present calculations of some of the key physical properties of microstructures of electrodes and separators present in lithium-ion batteries with porous electrode architectures. We analyze three-dimensional models of public domain real commercial porous anodes, cathodes and polyethylene (PE) separator, in order to characterize some of their microstructural properties. First, a pore space analysis of the binarized microstructure reveals the location and distribution of pores of various sizes, the overall porosity distribution and connectivity. Next, diffusion simulations using a random-walk method are performed to compute and accurately validate in-plane and through-plane effective transport coefficients and tortuosities, for different electrodes and calendaring levels. Single phase fluid flow simulations are performed using a commercial Lattice Boltzmann Method (LBM) solver to accurately validate the permeability of the microstructures. Next, multi-phase fluid flow simulations are done using this LBM solver to simulate the electrolyte in-filling process for various solvents. We predict that in-filling process may result in residual gas bubbles, which effect is shown in subsequent diffusion simulations to reduce the effective transport. The calculated McMillan numbers after in-filling show good agreement with experimental results. Next, we simulate the mechanical deformation of these microstructures under compressive strain using a finite element analysis (FEA) solver. This work illustrates how the use of multi-physics simulation tools can help to design these microstructures to satisfy the mechanical and electrochemical properties required of them.

Figure 1
Changes in Heat Generation during Degradation of Commercial Lithium-Ion Batteries
Authors: Spitthoff Lena , Wahl Markus Solberg , Vie Preben J. S. , Burheim Odne Stokke
Published: July 2022

The performance, lifetime and safety issues of lithium ion batteries (LIB) are strongly linked to temperature and many studies in the past three decades have been devoted to improving the understanding of thermal behaviour of LIB at cell and pack level1. We present ageing and diagnostic data of a commercial pouch LIB and present a thermal battery model. The thermal battery model is used to discuss changes in different heat generation sources alongside battery ageing measurements. It further allows for a differentiation between temperature induced and C-rate accelerated ageing.

A selection of LCO-graphite cells was aged and cycled in the full state-of-charge window at 5, 15, 25, 35 and 45°C. We compare constant current cycling with charge and discharge rates of 1 C, 2 C and 3 C, and constant power discharging. The cells were monitored in detail during the ageing including surface. The performance at lower C-rates, internal resistances and the changes in cell thickness were obtained as functions of changes in state-of-health. Thermal conductivity measurements were performed for the electrode material at end and beginning of life.

A 1D analytical thermal model is used for a discussion about the impact of the heat sources, the effect of a change in heat transport with ageing due to decreased thermal conductivities, and the impact of internal temperature gradients on ageing.

By utilizing the thermal battery model, it is possible to analyze the effect of the different heat sources on the overall battery temperature as well as degradation dependent changes in heat generation. The heat sources included in the model are the ohmic heat produced, heat production due to overpotential, and reversible entropic heat due to the electrode reactions, where the entropic heat can both act as a heat source and heat sink. The transfer of heat inside the battery is described using Fourier’s second law.

These heat and temperature effects allow further to differentiate between temperature induced and C-rate accelerated ageing. Together with evaluating the impact of temperature gradients over the cell compared to the maximum cell temperature, this allows to estimate the impact of an improved thermal management system.

References

1 Spitthoff, L.; Burheim, O.S.; Shearing, P.R. Temperature, Ageing and Thermal Management of Lithium-Ion Batteries. Energies 2021, 14, 1248. https://doi.org/10.3390/en14051248
Investigating Li Plating Distribution Caused By a Thermal Gradient through Modelling, Differential Voltage, and Post-Mortem Analysis
Authors: Tomaszewska Anna , Doel Robert , Parkes Michael , Offer Gregory James , Wu Billy
Published: July 2022

Relatively slow charging speeds are often quoted as a key barrier to customer acceptance of EVs. Currently, the charging rates are limited primarily by the risk of lithium plating. While traditionally lithium plating has been associated with low temperature charging, recent reports point to the fact that thermal heterogeneity can significantly affect the plating behaviour, sometimes making it more likely or accelerated in the warmer regions in a cell [1][2]. In EVs, through-plane thermal gradients often develop across individual pouch cells due to the widespread use of surface cooling, particularly during fast charging, when the heat generation rates are also increased. This work investigates the effects of such through-plane thermal gradients on the lithium plating behaviour using a multilayer 2D electrochemical-thermal model and high-rate cycling experiments. The results show that the thermal gradient can result in preferential plating in either the colder or warmer cell regions, depending on the average cell temperature and the activation energies of solid diffusion and lithium plating. While the diffusion rates are slower in the colder cell layers, warmer ones attract higher currents and either of these effects may dominate the plating behaviour. The experimental validation consists of differential voltage analysis, post-mortem visual examination and measurement of remaining capacity in coin cells harvested from Li-ion cells fast charged under uniform temperatures and under thermal gradients. The limitations of DVA as a technique to quantify lithium plating are highlighted. These stem from the fact that the quantification technique requires assuming that only lithium stripping and no de-intercalation takes place up to the differential voltage minimum. In reality, the current is divided between both reactions, and both the temperature and concentration of the metallic lithium may affect the rate of stripping, shifting the location of the minimum independently of the amount of lithium plated. The results shed light on the effects of thermal gradients on lithium plating behaviour in pouch cells and the challenges associated with quantifying plating with DVA.

References:

[1] – H. Wang, et al., “Underpotential lithium plating on graphite anodes caused by temperature heterogeneity”, PNAS 117, 29453-29461 (2020)

[2] – J. Sieg, et al., “Local degradation and differential voltage analysis of aged lithium-ion pouch cells”, J. Energy Storage 30, 101582 (2020)
(Henry B. Linford Award for Distinguished Teaching) The Role of Electrochemistry in Battery R&D
Authors: Winter Martin , Kasnatscheew Johannes , Heinemann Kerstin , Bartling Vanessa , Ellermann Leonie , Stolz Lukas
Published: July 2022

Encouragement and motivation of young talents and students to engage in the mesmerizing field of electrochemistry and in particular in electrochemical energy storage is of outmost prominence to generate sustainability in the battery community that is inevitable to guarantee manpower continuity in one of the biggest global challenges of mankind, i.e. climate change and depletion of fossil fuels. Lithium-based batteries are regarded as key energy storage technology for further breakthroughs in energy transition and mobility transition and related R&D.[1] Limitations in typical electrochemical performance criteria, e.g. energy/power density, fast charge capability and cycle life will likely require even more intense R&D efforts in the future.[2] Electrochemistry is not only the basic principle of battery cell operation, but a reliable and frequently underestimated in situ instrument for monitoring and diagnostics.[3, 4]

Alongside with its strong methodological capability, the fundamental principles of electrochemistry for the understanding of practical battery cells will be emphasized in this presentation. Fundamental electrochemical relations like Sand`s law, the Nernst equation, Ohm’s law and the rules of Faraday; and in reverse manner, their mindful use in electrochemical methodology can precisely indicate and forecast processes during battery cell application and thus realize a simple and systematic, but at the same time a very effective and impactful R&D approach.[5,6] Consequently, elucidating the role of electrochemistry in energy storage will build a bridge between (simple) electrochemical fundamentals and the rather complex practical behavior of state-of-the-art and future battery systems, thus serving as topical attraction for young talents to enter into one of the most relevant and fascinating fields of natural sciences and engineering.

Reference
s
:

[1] M. Winter, R. J. Brodd Chemical Reviews. 2004, 104, 4245-4269.

[2] R. Schmuch, R. Wagner, G. Hörpel, T. Placke, M. Winter Nature Energy. 2018, 3, 267-278.

[3] R. Nölle, K. Beltrop, F. Holtstiege, J. Kasnatscheew, T. Placke, M. Winter Materials Today. 2020, 32, 131-146.

[4] J. Kasnatscheew, M. Evertz, R. Kloepsch, B. Streipert, R. Wagner, I. Cekic Laskovic, M. Winter Energy Technology. 2017, 5, 1670-1679.

[5] L. Stolz, G. Homann, M. Winter, J. Kasnatscheew Materials Today. 2021, 44, 9-14

[6] F..Holtstiege, A. Wilken A, M. Winter M, T. Placke, Phys. Chem. Chem. Phys.,
2017
, 19, 25905-25918
(Invited) Initial Capacity Loss Mechanism of All-Solid-State Lithium Sulfide Battery Unraveled By in Situ Neutron Tomography
Authors: Yang Guang , Zhang Yuxuan , Self Ethan , Brahmbhatt Teerth , Bilheux Jean-Christophe , Bilheux Hassina , Nanda Jagjit
Published: July 2022

All-solid-state lithium metal batteries promise a specific energy >500 Wh/kg. A solid-state electrolyte (SSE) plays an irreplaceable role in reaching such an energy density goal. Among different SSE types, the sulfide and thiophosphate-based SSE has emerged as a prominent class of soft ionic conductors. Compared to their ceramic and oxide SSE counterparts, sulfide SSEs provide several favorable advantages, including a) high room temperature ionic conductivity up to 10 mS/cm that is comparable to liquid-based electrolytes; b) ductile and mechanically soft SSE that enables better processible and intimate contact with electrodes; and c) scalability with solution-based low-temperature synthesis route.

However, when paring with a high voltage cathode, such as lithium nickel manganese cobalt oxide (NMC), the (electro)chemical instability of the sulfide SSE at the electrode/SSE interfaces becomes a major challenge to tackle with. The interfacial instability can result in up to 50% initial capacity loss in a Li/sulfide SSE/NMC battery, thereby keeping the sulfide SSEs from commercialization. Herein, by using neutron computed tomography, we trace in situ lithium displacement in an all-solid-state battery composed of a 7Li anode, natLi3PS4(LPS) electrolyte, and a natLiNi0.8Mn0.1Co0.1O2 (NMC811) cathode. We show that after the first galvanostatic charge/discharge cycle, lithium accumulates at the LPS/NMC811 interface and preferably fills in the pre-formed cracks in the cold-pressed LPS SSE pellet. Such irreversible lithium displacement contributes to the initial capacity loss of the Li/LPS/NMC battery. Our findings suggest that to achieve high-capacity retention of an all-solid-state sulfide-based battery using an NMC cathode, the cathode/sulfide interface should be better engineered and the defects of the LPS pellet should be suppressed.

Acknowledgment

This research was conducted at Oak Ridge National Laboratory, managed by UT Battelle, LLC, for the U.S. Department of Energy (DOE) and is supported by Asst. Secretary, Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (VTO) through the Advanced Battery Materials Research (BMR) Program. This research used resources at High Flux Isotope Reactor, a DOE Office of Science User Facilities operated by the Oak Ridge National Laboratory.
Reinforcing the Li|Li1.3Al0.3Ti1.7(PO4)3 Interfacial Stability By an Ultrathin Multifunctional Polysiloxane-Based Single-Ion Conducting Polymer
Authors: Chen Zhen , Liang Hai-Peng , Stepien Dominik , Lyu Ziyuan , Zarrabeitia Maider , Kuenzel Matthias , Wu Fanglin , Kim Guk-Tae , Passerini Stefano , Bresser Dominic
Published: July 2022

Lithium metal is considered as one of the most promising anode candidates for high-energy batteries [1-3]. However, safety concerns induced by the formation of Li dendrites largely hinder the practical application of lithium-metal batteries [4]. It is anticipated that the use of non-flammable inorganic solid-state electrolytes can resolve these safety issues [5], but solid ceramic electrolytes generally suffer from poor physical contact with the electrode and poor electro-/chemical stability at the electrolyte|electrode interface [6].

Herein, we report on a thin and flexible hybrid electrolyte composed of NASICON-type Li1.3Al0.3Ti1.7(PO4)3 (LATP), a polymer binder, and a small amount of an ionic liquid-based electrolyte. To reinforce the interfacial stability between LATP and Li, we coat an ultrathin polysiloxane-based single-ion conducting polymer (PSiO) on the Li metal surface via a simple dip-coating method. The implementation of PSiO-coated Li (PSiO@Li) in symmetric PSiO@Li||PSiO@Li cells enables a substantial extension of the cycle life, yielding >2,000 h of stable lithium stripping-plating. The full-cells comprising PSiO@Li as the negative electrode, LiNi0.88Co0.09Mn0.03O2 (NCM88) as the positive electrode active material, and the aforementioned hybrid electrolyte exhibit substantially enhanced rate capability at high dis-/charge rates above 0.5C and greatly prolonged cycle life at 1C. The superior performance achieved herein is mainly attributed to: (1) the prevented direct contact between LATP and Li, thus avoiding the reduction of LATP and the formation of mixed ion-electron conducting interphases; (2) the regulated Li+ flux at the electrode|electrolyte interface, ensuring homogeneous Li+ stripping-plating; and (3) the promoted intimate contact between PSiO and Li via the formation of Si−O−Li bonds.

References

[1] T. Li, X.-Q. Zhang, P. Shi, Q. Zhang, Joule, 3 (2019) 2647-2661.

[2] B. Horstmann, J. Shi, R. Amine, M. Werres, X. He, H. Jia, F. Hausen, I. Cekic-Laskovic, S. Wiemers-Meyer, J. Lopez, D. Galvez-Aranda, F. Baakes, D. Bresser, C.-C. Su, Y. Xu, W. Xu, P. Jakes, R.-A. Eichel, E. Figgemeier, U. Krewer, J.M. Seminario, P.B. Balbuena, C. Wang, S. Passerini, Y. Shao-Horn, M. Winter, K. Amine, R. Kostecki, A. Latz, Energy Environ. Sci., 14 (2021) 5289-5314.

[3] S. Wang, P. Xiong, J. Zhang, G. Wang, Energy Storage Materials, 29 (2020) 310-331.

[4] Z. Yu, Y. Cui, Z. Bao, Cell Rep. Phy. Sci., 1 (2020) 100119.

[5] S. Xin, Y. You, S. Wang, H.-C. Gao, Y.-X. Yin, Y.-G. Guo, ACS Energy Lett., 2 (2017) 1385-1394.

[6] A. Banerjee, X. Wang, C. Fang, E.A. Wu, Y.S. Meng, Chem. Rev., 120 (2020) 6878-6933.
Pursuing of Equi-Atomic Electrodeposited Cu-Co-Fe-Ni Film
Authors: Sun Yunkai , Zangari Giovanni
Published: July 2022

Composition control of multicomponent electrodeposited alloy films is very challenging. For example, non-linearity between the deposit composition and bath constitution could occur in alloy electrodeposition systems containing Fe and Ni, due to the anomalous codeposition phenomena (which usually means electrodeposition kinetics is controlled by the reduction of intermediates at the surface of cathode rather than the mass-transfer in the diffusion layer). On the other hand, it is still uncertain if the composition of alloy electrodeposition system is chaotic within the experimental errors in the electrolyte preparation and electrodeposition cell setup.

In this presentation, we will introduce some recent explorations in the composition control of the quaternary alloy Cu-Co-Fe-Ni. The initial stage composition will be investigated with cross-section SEM-EDS line-scans, whereas the nonlinearity will be explored with electrodeposition at a fixed duration but different applied potentials, concentrations of depositing species, and supporting electrolytes with different pH buffer capability.
Effect of Cetrimonium Bromide As an Additive on the Morphology and Mechanical Properties of the Electrodeposited Coatings Developed from Ethaline-Based Cyanide-Free Bath
Authors: Satpathy Bangmaya , Sau Arghyadeep , Jena Sambedan , Das Siddhartha , Das Karabi
Published: July 2022

In the present study, a non-aqueous ethaline-based electroplating bath was prepared without the addition of cyanide complexing agents. Gold coatings were prepared via DC galvanostatic route from the developed bath with and without the presence of cetrimonium bromide (CTAB) as an additive. Electrochemical studies (EIS and LSV) provided a detailed insight regarding the metal-complex interaction and the reduction occurring during the electrodeposition process. A time-dependant UV-Vis spectroscopy was carried out to study the stability of the developed bath. Glancing-angle incidence (GI) XRD and EDS analysis of the developed coatings substantiated the presence of pure gold, without any complex. The coatings deposited with the presence of additive had a relatively higher concentration of gold as compared to the coatings without any additive. The SEM and AFM studies were carried out to study the effect of CTAB on the morphology of the coatings. The coatings deposited from the bath containing CTAB had a smooth surface and the AFM studies indicated that they had a low roughness. The coating thickness was confirmed from cross-section SEM. Coatings deposited with the presence of CTAB had a hardness value of 293±6 VHN and those carried out without CTAB showed a lower hardness of 214±9 VHN. The coating deposited with the presence of CTAB was compact, had a bright golden appearance and a good adherence with the underlying substrate. The gold coatings deposited without the presence of CTAB had a dull appearance and the coatings lacked uniformity. The preliminary adherence of the coatings was evaluated using the scotch-tape pull-out test.

Fig. SEM micrographs of coating deposited via DC galvanostatic route from ethaline-based gold electroplating bath (a) without CTAB, and (b) with CTAB.

Figure 1
(Digital Presentation) Znni Electroplating from an Ethylene Glycol Based Non-Aqueous Electrolyte for Corrosion Protection
Authors: Bernasconi Roberto , Firtin Fatma Godze , Kahyaoglu Buse , Nobili Luca , Magagnin Luca
Published: July 2022

ZnNi alloys containing Ni in the 15 - 25 % wt. range have recently attracted the attention of researchers due to their interesting corrosion properties [1]. These materials, when deposited in the form of thin films, find application in a large number of industrial fields: oil and gas, automotive and constructions. ZnNi is normally electrodeposited from aqueous solutions, specifically alkaline cyanide-free or acidic chloride baths. In these electrolytes, plating takes place following a typical anomalous mechanism where the less noble metal (zinc) deposits preferentially [2].

Even though ZnNi plating from water based solution is already implemented at the industrial scale, alternative deposition approaches have been developed in the last few years to further improve ZnNi plating performances. In particular, the use of non-aqueous electrolytes has been investigated by virtue of their significant advantages over water based solutions: wider electrochemical windows, reduced side reactions and low vapor pressure. ZnNi electrodeposition has been attempted from a great variety of such novel baths, mainly including II and III generation ionic liquids [3, 4].

The present work investigates the use of non-aqueous ethylene glycol based electrolytes for the deposition of ZnNi alloys containing Ni in the 15 - 25 % wt. range. The use of ethylene glycol as solvent introduces many advantages with respect to aqueous solutions: low oxygen contamination, high deposits purity and no pH dependance [5]. ZnNi codeposition from ethylene glycol baths containing ZnCl2 and NiCl2 was studied employing cyclic voltammetry and thin layers were deposited under potentiostatic control. Deposition potential was varied and its influence on final composition and morphology was determined. Compositional data evidenced the occurrence of a potential dependent anomalous codeposition mechanism analogous to the one reported in water based electrolytes. Addition of an additive (NH4Cl) to enhance surface morphology was attempted as well [4]. Phase composition was investigated using XRD and the results obtained demonstrated the presence of a metastable γ-ZnNi phase, which has already been observed in the case of ZnNi plated from alkaline aqueous solutions [6]. Finally, corrosion behavior of the ZnNi layers obtained from ethylene glycol was assessed and compared with equivalent coatings deposited from commercial ZnNi aqueous solutions.

[1] M. Gavrila et al., Surf. Coat. Technol. 123 (2-3), 164-172 (2000)

[2] G. Roventi et al., J. Appl. Electrochem. 30 (2), 173-179 (2000)

[3] K. K. Maniam et al., Appl. Sci. 10, 5321 (2020)

[4] S. Fashu et al., Trans. Nonferrous Met. Soc. China 25 (6), 2054-2064 (2015)

[5] G. Panzeri et al., Electrochim. Acta 271 (1), 576-581 (2018)

[6] S. Ieffa et al., Trans. Inst. Met. Finish. 94, 321-324 (2014)
Understanding Key Limiting Factors of Electrode and Cell Designs in Solid-State Lithium Batteries
Authors: Yim Chae-Ho , Abu-Lebdeh Yaser
Published: July 2022

Solid-state batteries (SSBs) use solid electrolytes (SE) to replace flammable liquid electrolytes that result in safer batteries with increased energy density enabled by lithium metal as an anode. Even though there have been recent major breakthroughs at the material level and some at the cell level, there are still many more challenges to overcome that are mostly related to the solid-solid interfaces besides the grand challenge of manufacturing these type of batteries with or without existing manufacturing processes with the promised energy density ( > 400Wh/Kg) at targeted low costs (< 100$/KWh). For this to happen, it is important to look into all the changes that need to be made at the material, electrode and cell levels compared to what is currently used in Li-ion cells and critically evaluate their impact on the cell energy density. In this work, we have first used an equation that we have previously modified and used to calculate the impact of Si content in Si-graphite composite on the full-cell energy density (2) to evaluate the impact of the following parameters (type of anode-or no anode- and cathode materials. N/P ratio, thickness of SE and most importantly the composite cathode formulation on the full-cell energy density. In the latter, we have evaluated the thickness of two electrodes, amount and volume of cathode active material, and amount of catholyte). We will present the impact of each of the above-mentioned factors on the cell energy density supported by data from half and full cells using composite cathodes coupled with and without lithium metal as an anode.

References:

(1) Mauro Pasta et al 2020 J. Phys. Energy 2 032008.

(2) Chae-Ho Yim, Svetlana Niketic, Nuha Salem, Olga Naboka and Yaser Abu-Lebdeh, 2017, J. Electrochem. Soc. 164 A6294.
Azo-Integrated Covalent Organic Frameworks As Electrodes for Lithium-Ion Batteries
Authors: Singh Vikram , Kim Jaewook , Kang Bora , Moon Joonhee , Kim Sujung , Kim Woo Youn , Byon Hye Ryung
Published: July 2022

Covalent Organic Frameworks (COFs) are two-dimensional, porous, and crystalline organic structures. The well-established frameworks provide ordered mesopores, structural stability, high density, and negligible solubility, which are particularly attractive for battery electrodes. By integrating a redox-active azo group to COFs, we designed positive organic electrodes and applied these electrodes for nonaqueous Li-ion batteries. The azo group can undergo two electrons transfer, whereas its reversibility and stability are highly dependent on adjacent functional groups [1,2]. We developed three azo-integrated COFs with three different linkages, -ketoenamine, imine, and thiazole-fused ring. These azo-COFs had identical hexagonal P6/m space groups, ~3 nm of pore size, and 600~1000 m2 g–1 of surface area. However, the redox chemistries of azo groups were remarkably distinct from the linkages. The-ketoenamine and imine based azo-COFs showed irreversible azo reactions, resulting in poor capacity retention. In contrast, the fully conjugated COF containing the thiazole-fused ring rendered excellent cycling stability showing 5000 cycles at 10 C. The reversible azo reaction was also demonstrated by using operando Raman spectroscopy. This result corresponded to the single and sharp redox wave at a formal potential of ~1.7 V vs. Li/Li+, suggesting the one-step two electrons transfer. The solid electrolyte interphase (SEI) was formed at the initial cycles only, which could protect the COF surface and inhibit the continuous decomposition of the electrolyte solution. Electrochemical impedance spectroscopy (EIS) revealed the low charge transfer resistance (~18 Ω), which decreased further after 20 cycles (~6 Ω). The mass transport region in the EIS curve was retained, indicating the access of Li+ to the bulk COF structure through mesopores for cycling. In the presentation, I will discuss the details of COF designs and the role of linkages enhancing the reversible and stable redox reactions in Li-ion cells.

References:

[1] Luo, C., Borodin, O., Ji, X., Hou, S., Gaskell, K.J., Fan, X., Chen, J., Deng, T., Wang, R., Jiang, J. and Wang, C. PNAS, 2018, 115, 2004-2009.

[2] Luo, C., Xu, G.L., Ji, X., Hou, S., Chen, L., Wang, F., Jiang, J., Chen, Z., Ren, Y., Amine, K. and Wang, C., Angew. Chem. Intl. Edn.
2018, 57, 2879-2883.

Figure 1
Development of a LiMnFePO4 / Li4Ti5O12 2Ah Pouch Cell: An Example of the Effective Integration of New Materials
Authors: Dontigny Martin , Perea Alexis , Asakawa Yuichiro , Zaghib Karim , Daigle Jean-Christophe
Published: July 2022

One of the most promising approaches for limiting climate change is the use of alternative and greener sources of energy (wind, solar, etc.). The electricity generated from these sources fluctuates, however, and a storage solution is needed. The advent of energy storage for wind farms, solar plants, etc., requires a new generation of batteries. It is therefore imperative that a battery with high energy density, a longer life cycle and improved safety be developed.

In this paper, we describe our efforts to develop a safe and long-life cycle LiMnFePO4 (LMFP)/Li4Ti5O12 (LTO) 2Ah pouch cell. One of the major challenges faced in this pursuit was gas evolution during cycling. Various side reactions with active materials resulted in the generation of gas during cycling. To circumvent this, we implemented several mitigation strategies. To combat electrolyte degradation (1.0 M LiPF6 in carbonate solvents) due to Mn2+ dissolution in LMFP, we integrated a new class of polymer as a binder in the cathode preparation, which effectively decreased the degradation during cycling. This polymer also has high voltage stability.1 At the battery’s negative electrode, we developed a new carbon coating method on LTO that minimizes electrolyte degradation and optimizes high C-rate preformances, especially fast charging performances.2 Although these new materials reduce gas evolution, they do not eliminate it. Therefore, we developed the first polymer capable of trapping the carbon dioxide, major component of gases generated during cycling and, in turn, preventing pouch cell inflation. This polymer was integrated in a pouch cell in the form of an insoluble trapping sheet.3 Although relatively simple, this technology made the pouch cells safer. This unique approach is versatile and can be implemented in pouch cells with any type of chemistry when gas scavenging is required. The 2Ah pouch cells did not experience any inflation during extensive cycling and aging. Cells cycled more then 750 cycles at 45oC with a rate of 1C – 1C before reaching 80% retention capacity.

Reference

(1) Daigle, J.-C.; Asakawa, Y.; Zaghib, K. Polymer additives and their use in electrode materials and electrochemical cells. WO2020061710A1, 2020.

(2) Daigle, J.-C.; Asakawa, Y.; Beaupre, M.; Gariepy, V.; Vieillette, R.; Laul, D.; Trudeau, M.; Zaghib, K. Boosting Ultra-Fast Charge Battery Performance: Filling Porous nanoLi4Ti5O12 Particles with 3D Network of N-doped Carbons. Sci. Rep.
2019,
9 (1), 1-9, DOI: 10.1038/s41598-019-53195-1.

(3) Daigle, J.-C.; Asakawa, Y.; Perea, A.; Dontigny, M.; Zaghib, K. Novel polymer coating for chemically absorbing CO2 for safe Li-ion battery. Sci. Rep.
2020,
10 (1), 10305, DOI: 10.1038/s41598-020-67123-1.
(Invited) Battery Design for Fast Charging
Authors: Li Jianlin
Published: July 2022

Lithium-ion batteries (LIBs) has been broadly applied in electric vehicles (EVs) and the market adoption of EVs can be further improved with enhanced fast charging capabilities. The state-of-the-art chemistries, such as LiNixMnyCo1-x-yO2 (NMC) and graphite, are capable for fast charging. However, the electrodes are limited to thin coating due to mass transport limitation, which results in low energy density and high cost [1]. For example, the United States Department of Energy (DOE) issued a call for proposal in 2017 to enable extreme fast charging with a target of cell energy density higher than 180 Wh/kg which is much lower than that under normal application.

The energy density of LIBs depends on the materials properties and cell engineering. In this presentation, the impact of cell design on energy density under fast charging will be discussed. Specifically, design in electrodes, current collectors, electrolyte, and separator will be elaborated to show their correlation to fast charging application [2-3].

Acknowledgment

This research at Oak Ridge National Laboratory (ORNL), managed by UT Battelle, LLC, for the U.S. Department of Energy under contract DE-AC05-00OR22725, was sponsored by the Office of Energy Efficiency and Renewable Energy (EERE) Vehicle Technologies Office (VTO) and Advanced Manufacturing Office (AMO).

References

[1] Colclasure, A. M.; Dunlop, A. R.; Trask, S. E.; Polzin, B. J.; Jansen, A. N.; Smith, K. Requirements for Enabling Extreme Fast Charging of High Energy Density Li-Ion Cells while Avoiding Lithium Plating. J. Electrochem. Soc.
2019, 166, A1412-A1424.

[2] Parikh, D.; Christensen, T.; Li, J.; Elucidation of separator effect on energy density of lithium-ion batteries, J. Electrochem. Soc.
2019, 166 (14), A3377.

[3] Parikh, D.; Christensen, T.; Li, J.; Correlating the influence of porosity, tortuosity, and mass loading on the energy density of LiNi0. 6Mn0.2Co0.2O2 cathodes under extreme fast charging (XFC) conditions, Journal of Power Sources, 2020, 474, 228601.