bluuebunny/crossref_metadata_2025_split huggingface dataset:
Quantifying the Structure and Chemistry of Semiconductor Devices with the Latest Advancements in Scanning Transmission Electron Microscopy
Authors: LeBeau James 
Published: November 2022

Electron microscopy has been revolutionized by the advent of the aberration corrector and advances in detector both for imaging and spectroscopy. Aberration correction dramatically improved spatial resolution into the sub-ångstrom regime, while new detectors have unlocked information about materials that was previously only imaginable.While these recent advances have proven essential to the atomic scale characterization of materials, many measurements have remained largely semi-quantitative. In particular, accuracy and precision for scanning transmission electron microscopy (STEM) was significantly hampered by the presence of sample drift and scan distortion. Until recently, this limitation has obscured the capabilities to characterize minute changes to the atomic structure that can ultimately define material properties.
In this talk, we will introduce revolving scanning transmission electron microscopy (RevSTEM) for the characterization of semiconductors. The method uses a series of fast-acquisition STEM images, but with the scan coordinates rotated between successive frames. This scan rotation introduces a concomitant change in image distortion that is then used to analyze the sample drift rate and direction. Multiple case studies will be presented to demonstrate the power of this technique to characterize electronic materials. For example, we will show how picometer level precision and accuracy enabled the capability to directly quantify ferroelectric HfO2 thin films. We will also show how RevSTEM images can be used to accurately determine crystallographic parameters in real-space, and to determine the structural origins of polarization.
When combined with modern spectroscopy tools, the technique can directly inform growth mechanisms in AlN based materials for fabrication of quantum well structures. Specifically, We will show the interface quality between various AlGaN/AlN quantum wells using a combination of high-angle annular dark-field (HAADF) imaging and energy dispersive X-ray spectroscopy (EDS). We will show that we can directly measure the lattice parameters for each layer and how they vary across each AlN/AlGaN interface. Using EDS, we correlate the lattice parameters and lattice parameter values to the chemical composition in each layer. We show that throughout multiple quantum well structures, there is an asymmetrical interface with a diffusion of Ga on one side of the AlGaN layer. Further, we will discuss fluctuation in the composition present throughout each layer and the role on the local strain distribution.
Influence of Aviation Conditions on Lithium-Ion Batteries
Authors: Hoenicke Pia , Khatri Roni , Willich Caroline , Bauer Christiane , Osama Mohamed 
Published: November 2022

Stopping climate change and global temperature rise needs a determined course of action in several technology fields and the development of ZERO-CO2 aircrafts and low emission battery-ICE aircrafts, as well. Batteries in hybrid-electric or fully-electric aircrafts are an option to decrease emissions. The battery requirements for the aviation sector regarding specific energy, energy density and safety are high. Lithium-ion batteries are today the only commercially available technology to meet these requirements, but adequate technology readiness is only proven for the automobile sector while TRL levels 8 and 9 for implementation readiness of batteries in the aviation sector is still ongoing. A crucial aspect for aviation applications is the operation behavior in high altitude including low temperature, wide humidity ranges and especially low pressure. There is little published information available on the effects of low pressure on battery performance. Therefore, different commercially available lithium-ion batteries were tested from atmospheric pressure down to 250 hPa, which corresponds to a flight altitude up to 10,000 m, according to the International Standard Atmosphere (ISA). Since NMC and NCA cathode materials are promising for aviation due to their high specific energy, and LFP cells are promising because of their high safety, the following batteries were selected:

20 Ah HP602030 LFP cylindrical cell (EAS Batteries GmbH, GER).

10 Ah HE 341440 NCA cylindrical cell (EAS Batteries GmbH, GER).

12 Ah SLPB065070180 NMC pouch cell (Kokam Co. Ltd., KOR)

To examine the influence of pressure on the battery behavior, constant current discharge tests at 1C 0.5C and 2C rates as well as impedance measurements in 10% SOC steps were performed in a climate controlled low-pressure chamber. The batteries were operated under different temperatures and in controlled low pressure. The pressure was first set to atmospheric pressure as a reference and then lowered to 750 hPa, 500 hPa and 250 hPa. To further examine altitude influences, current cycles and impedance spectroscopy were performed at different temperature and humidity values.
The behavior of the cylindrical cells showed hardly any pressure dependency, while the examined pouch cell’s behavior did show a pressure dependency.
All batteries showed strong temperature dependency but hardly any humidity dependency.
In this presentation the influence of pressure, temperature and humidity on voltage, capacity, resistance and impedance of the afore mentioned batteries will be discussed. The batteries are compared regarding their aviation applicability with special respect to low pressure. The parameters for each environmental condition can then be used to parameterize a battery model suitable for aviation applications.
Industrial Perspectives on Innovation: Sustainability, Safety, Scalability, and Advanced Performance
Authors: Yakovleva Marina , Fitch Brian , Xia Jian 
Published: November 2022

Industry continues to look forward to innovative and to sustainable solutions that can improve battery performance, safety, and manufacturing efficiency. Livent is looking forward to bringing LIOVIX™ to the market as a product to help meeting these growing requirements while opening pathways for the development of next generation battery technology.
LIOVIX™, proprietary lithium metal product, is a unique printable formulation of lithium metal and other specialty materials that can improve the performance of lithium-ion batteries, reduce manufacturing costs, and enable the next generation of battery technology, all while enhancing safety and sustainability.
LIOVIX™ can be printed on a battery’s anode during electrode manufacturing in a process called pre-lithiation. Pre-lithiation employs an external, sacrificial source of lithium to offset the first cycle loss of lithium due to SEI formation allowing more efficient use of lithium from the cathode and raising the cell energy density. However, pre-lithiation techniques that are scalable at giga-factory throughput speeds have yet to be demonstrated. LIOVIX™ technology is easily scalable using industry standard coating and printing equipment and is adaptable to any anode or cathode chemistry where an independent source of lithium is required. LIOVIX™ can be used in anodes with a range of silicon content, because lithium loading can be accurately controlled based on the applications’ requirements. Incorporation of this technology has led to higher columbic efficiency at the first cycle, better cell capacity, and longer life batteries. In fact, the application of LIOVIX™ has been demonstrated to improve a battery’s output and to extend its useful life for a variety of battery chemistries (Figure 1).
LIOVIX™ is an important technology for the development and commercialization of solid-state batteries using lithium metal. These next generation batteries will address many of the challenges and limitations of today’s liquid electrolyte-based battery systems. LIOVIX™ can be directly printed on current collectors and can act as an anode in solid state batteries. It can also be printed on other anode material to improve the first cycle columbic efficiency and cell performance. It can reduce the interface resistance between anode and solid electrolyte layer.
Commercialization of battery systems that use metallic lithium anodes is strongly dependent on the industry’s ability to manufacture these anodes cost effectively at scale. Using LIOVIX printable lithium technology thin lithium foils in the range of 10um – 30um have been demonstrated at the desired width.

Figure 1
Development of Earth-Abundant Cathodes for Vehicle Applications and Beyond
Authors: Gutierrez Arturo , Chen Jiajun , Vu Anh , Lin Yulin , Wen Jianguo , Dogan Fulya , Balasubramanian Mahalingam , Croy Jason R. 
Published: November 2022

The predicted growth in electrification of the grid-storage and transportation sectors has seemingly left the research community a significant responsibility in developing a more robust portfolio of materials solutions. Specifically, it has become clear that beyond simply meeting/exceeding the current technical requirements, new technologies would do well to align with the goals of sustainable development in supporting market growth. Current state-of-the-art, Li-ion cathodes, based heavily in Ni, will continue to play an important role. However, alternatives to these chemistries will be critical in diversifying supply chains and expanding the available portfolio of electrode materials towards a more sustainable future. Among the potential candidates for next-generation cathodes are Lithium- and Manganese-rich oxides. These oxides remain attractive because of their intrinsically high, specific capacities/energies and the economic benefits they offer through earth-abundant, Mn-rich (>50%) compositions.
This presentation will discuss research and development efforts at Argonne National Laboratory aimed at advancing cathode materials that are rich in manganese and have the potential to be cost competitive for electric vehicle applications and beyond. Research efforts into mitigation of issues related to several identified critical barriers, such as impedance, will be discussed.
High Throughput Studies of Li-La-Zr-O Garnet Solid Electrolytes
Authors: Anderson Ethan , Jonderian Antranik , McCalla Eric 
Published: November 2022

Development of next-generation Li-ion batteries has increasingly focused on all-solid batteries employing either ceramic, polymer, or glass electrolytes in order to address shortcomings in currently commercialized liquid electrolyte Li-ion batteries including safety, limited lifetime, and lower energy densities resulting from instability with respect to Li metal anodes.[1] Lithium lanthanum zirconium oxide (LLZO) is a leading candidate for solid Li-batteries due to its high Li-ion conductivity, stability in air and against Li metal, and compatibility with high-voltage cathodes.[2],[3]

Despite significant progress being made, our understanding of LLZO is limited by the relatively small number of compositions which have been studied; especially considering the leading contender is a pseudo-quaternary oxide (Ga-doped LLZO) and many studies are now utilizing multiple dopants.[4]

Herein, we have applied a high-throughput methodology for synthesizing, characterizing, and testing sets of 64 LLZO electrolytes at the mg-scale. We employ a citrate sol-gel synthesis method whereby reagent solutions are dispensed across a well-plate to give a composition gradient. After drying the samples and burning off the citrates, the resulting powders are pressed into pellets using a custom-made 64-pellet die and the pellets are sintered at the desired temperature. The high-throughput characterization techniques utilized include powder X-ray diffraction, electrochemical impedance spectrometry and electrochemical cycling in order to test electrolyte stability; with each method performed on up to 64 samples simultaneously.
Using our methodology, we have studied over 700 samples to produce a full phase stability diagram for the Li-La-Zr-O pseudoternary system. We find that within the Li-La-Zr-O system, there is significant solubility of Li into the La2Zr2O7 pyrochlore structure commonly found as an impurity in LLZO synthesis due to lithium loss. We also find that LLZO appears as both tetragonal and cubic forms throughout the system, with the cubic LLZO appearing in an extremely restricted region that is difficult to access as pure phase due to lithium loss, while excess lithium leads to the tetragonal LLZO. Li conductivity measurements show that both cubic and tetragonal undoped LLZO have similar bulk conductivities, but there is only a limited region near the formal Li7La3Zr2O12 composition where grain boundary conductivity is high. Our methodology is also applied to a comprehensive doping study where over 40 different dopants are evaluated and promising dopants are tested in co-doped compositions.

[1] D. Aurbach et al., Electrochimica Acta
2004, 50, 247-254.

[2] Q. Liu, et al., J. Power Sources
2018, 389, 120-134.

[3] T. Thompson, et al., ACS Energy Letters
2017, 2, 462-468.

[4] F. Zheng, et al., J. Power Sources
2018, 389, 198-213.
Boron-Doped Methylated Amorphous Silicon for Negative Electrodes in Li-Ion Batteries
Authors: Phung Tram Ngoc , Feng Yue , Petitjean Timothée , Henry-de-Villeneuve Catherine , Rosso Michel , Ozanam François 
Published: November 2022

In spite of its outstanding capacity for alloying with lithium, silicon cannot be practically used as a negative electrode for Li-ion batteries: its large volume expansion upon lithiation leads to a poor capacity retention [1]. Promising results have been obtained by incorporating methyl groups in amorphous silicon (methylated amorphous silicon). This material exhibits an improved stability upon electrochemical cycling while keeping a capacity close to that of pure silicon [2]. However, the conductivity of methylated amorphous silicon may be a strong limitation, especially at high methyl content: for example, 10% methylated amorphous silicon is 10000 more resistive than pure amorphous silicon.
Doping is a well-known method to enhance the electronic conductivity of semiconductors, even if the dopant activity is lower in amorphous semiconductors than in crystalline ones. 2% boron doping increases the conductivity of 10% methylated amorphous silicon by five orders of magnitude compared to the undoped material.
Boron doped methylated silicon thin films (100nm thick) with various methyl content were cycled in the range 0.025V – 1V at C/2 rate (electrolyte: LP30 with 5%FEC). 10% methylated amorphous silicon with 2% boron doping exhibits a capacity retention of 70% after 500 cycles of full lithiation/delithiation, an improved performance as compared to the undoped material (see Figure 1a). Interestingly, boron doping allows for using higher methyl content without demanding pre-conditioning procedures for the electrochemical cycling of the material. The stability upon cycling is found to be further increased for 15% and 20% methylated electrodes, with a capacity retention exceeding 80% over 1000 cycles of full lithiation/delithiation (Figure 1b). This figure comes at the expense of a decreased total capacity (which remains 3 to 4 times larger than that of the current carbon electrodes). The SEI evolution and structural changes are currently investigated using operando ATR FTIR and ex-situ Raman spectroscopies, in order to rationalize the factors limiting the Coulombic efficiency to 99.7%. References
[1] M. N. Obrovac, L. Christensen, D. B. Le and J. R. Dahn, J. Electrochem.Soc,
154, A849-A855 (2007).
[2] L. Touahir, A. Cheriet, D. Alves. Dalla Corte, J.-N. Chazalviel, C. Henry-de-Villeneuve, F. Ozanam, I. Solomon, A. Keffous, N. Gabouze and M. Rosso, J. Power Sources,
240, 551-557 (2013).

Figure 1
Binder Effect on Electrochemical Performance of Silicon Anodes
Authors: Sun Fei , Rosborough Niccolo , Clarke Nathan , Smith Stacey , Mazzeo Brian A. , Wheeler Dean 
Published: November 2022

Binder is a crucial component of high-capacity silicon anodes. It allows the active material to cohere to itself and surrounding materials. In the past few years, there have been divergent conclusions on the cell performance of anodes using water-based PAA vs. LiOH-PAA binder [1-3]. While there is agreement that LiOH-PAA facilitates the coating process, cell performance between these two binders is not settled.
The difference in cell performance may be due to the pH value or the extra Li+ in the binder, both of which change when LiOH is added to PAA. In this work we examined these two factors separately to determine their effect on cell performance. Our hypothesis is that the extra Li+ could facilitate ion transfer and the low pH could affect current collector corrosion and silicon oxidation. NH3(aq) is used to adjust the binder slurry pH and experimental results are compared between NH3-PAA and LiOH-PAA electrodes otherwise made with the same pH value. Similarly, we compared performance of NH3-PAA anodes with different pH values.
Multiple experiments were done to compare aspects of cell performance. Overall electrochemical performance was examined by cell cycling. Ionic conductivity was determined by an impedance test. Contact resistances to the current collector were measured with an apparatus developed in our lab. Silicon oxidation state was determined by XRD. Morphology of the anode can be compared by SEM.
In our cycling results silicon half cells with LiOH-PAA binder had a 10% higher capacity than those with PAA binder (Fig. 1), all other factors being constant. And the LiOH-PAA film had a lower impedance value which confirms the hypothesis that extra Li+ could facilitate ion transfer. The PAA anode had a lower contact resistance to the current collector than did the LiOH-PAA anode. This result agrees with Xiong’s work [3], which claims that the corrosion of current collector when using PAA slurry could form a more rigid coating surface and thus lead to the surface cracking and lower the capacity. Other parts of this work including cycling performance and XRD are still in progress and will be reported.

Hays, K.A., et al., Journal of Power Sources, 2018. 384: p. 136-144.

Hu, B., et al., Journal of Power Sources, 2019. 416: p. 125-131.

Xiong, J., et al., ACS Applied Materials & Interfaces, 2021. 13(24): p. 28304-28323.

Figure 1
Advances in the Aqueous Processing of Ni-Rich Positive Electrodes
Authors: Radloff Sonja , Carbonari Gilberto , Scurtu Rares-George , Hölzle Markus , Wohlfahrt-Mehrens Margret 
Published: November 2022

A sustainable and environmental friendly production process of the battery components is a crucial factor for a successful contribution of Li-ion batteries to a more sustainable energy supply. For carbon-based anodes the eco-friendly, water-based processing is already widely established, whereas the same procedure still poses several challenges for cathode materials, especially those with high Nickel content. One major challenge is the detrimental side-reaction of Ni-rich cathode active materials (CAM) with water, creating hydroxide and carbonate species which increase the pH of the paste to above 12. Consequently, the Al foil is corroded during the coating process. Therefore, it is essential to control the paste’s pH before casting the paste on the substrate Al foil. This step becomes more challenging the longer the electrode mixing and coating procedure takes. On top of this, a promising way of improving the aqueous-based processing is to identify a suitable water-based binder system to improve the electrochemical cycling stability.
We present the application of a variety of different water-based binders, all used in combination with carboxymethyl cellulose (CMC) as thickening agent. The paste pH is controlled by adding H3PO4. Electrodes with industry relevant areal capacities of up to 3 mAh/cm2 are electrochemically evaluated in full pouch cells. The long-term cycling stability determined with 1 C charge/discharge was highly dependent on the binder system. The best electrodes reached an excellent capacity retention of up to 88% after 1000 cycles. The NMP-based reference electrode reached 91%.
The investigation of the aged cells via post mortem analysis suggests that the main source of cell aging is the cathode electrode. According to scanning electron microscopy data, no stronger cracking of the secondary CAM particles and no enhanced dissolution of transition metals were observed for the aqueous cathodes. However, a stronger rise in charge-transfer impedance was observed for the aged, water-based cathodes. This suggests that the formation of a blocking surface layer is the major reason for a stronger performance decay with increasing cycle number.

Acknowledgment
The presented work was financially supported by the project DigiBattPro4.0 BW (3–4332.62-IPA/69) by the Ministry of Economic Affairs, Labour and Housing Baden-Württemberg and by the project DigiBattPro4.0 BMBF funded by the German federal ministry of education and research Baden-Württemberg (03XP0374D).
Ultrafine-Grained Ni-Rich Layered Cathode for High-Performance Li-Ion Batteries
Authors: Park Geon-Tae , Noh Tae-Chong , Sun Yang-Kook 
Published: November 2022

Currently, Li-ion batteries (LIBs) are the main power source for electric vehicles (EVs) because of their high energy density, excellent rate performance, and long cycle life. However, even EVs that are powered by state-of-the-art LIBs are unable to meet the driving range offered by internal combustion engine vehicles (ICEVs), which is typically 600–800 km.1 The properties of LIBs are strongly related to the nature of positive electrodes (cathodes), and thus, the selection of appropriate cathodes is of paramount importance. Currently, Ni-rich layered LiMO2 (M = Ni, Co, Mn, and/or Al) compounds are considered ideal cathode materials for EV batteries because their high capacity enables EVs to achieve high mileage per charge. Although Ni-rich layered cathodes are advantageous in terms of energy density and material cost, in general, they have considerably decreased cycling lifetimes with inferior thermal stabilities, which hinder their commercialization. The inherent structural instability of Ni-enriched layered oxide cathodes, particularly in the deeply charged state, leads to a build-up of mechanical strain.2 The strain build-up causes the nucleation and propagation of microcracks, which enable electrolyte infiltration and accelerate structural deterioration, which has plagued attempts to stabilize the cycling performance of Ni-rich layered cathodes.3 In this study, we demonstrate that limiting the primary particle size of the cathode resolves the capacity fading problem as nano-sized primary particles effectively relieve the high internal strain associated with the phase transition near charge end and fracture-toughen the cathode. Particle size refinement, achieved by inhibiting the grain growth during lithiation through the introduction of a high-valence dopant, imparts the necessary mechanical toughness to counter the high internal strain associated with the phase transition near charge end. The Li[Ni0.95Co0.04Mn0.01]O2 cathode, whose microstructure is engineered to mitigate the mechanical instability of Ni-rich layered cathodes, represents a next-generation, high energy-density cathode with a long cycle life and fast charging capability.

Reference
s
:

[1] K. B. Naceur, Tracking Clean Energy Progress (International Energy Agency, 2016).
[2] H.-H. Ryu, K.-J. Park, C. S. Yoon and Y.-K. Sun, Chem. Mater. 30 (2018) 1155–1163.
[3] G. W. Nam, N.-Y. Park, K.-J. Park, J. Yang, J. Liu, C. S. Yoon, Y.-K. Sun, ACS Energy Lett. 4 (2019) 2995–3001.