bluuebunny/crossref_metadata_2025 huggingface dataset:
Optimization of Loading Content of Li4Ti5O12-Hard Carbon Composite Anode for the Fast Charging Li-Ion Battery
Authors: Saneifar Hamidreza , Liu Jian
Published: July 2022

Fast charge of lithium-ion batteries (LIBs) needs anode and cathode materials operating at high current densities. Li4Ti5O12 (LTO) can enable fast lithium ion (Li+) transport due to its 3D crystal structure. Nonetheless, this material suffers from low specific capacity and high operating voltage. In contrast, Hard Carbon (H.C) with high specific capacity and low practical voltage is one of the promising anode materials for high-energy lithium-ion batteries. However, practical application of this material is compromised with its slow kinetic, and reduced cycling performance associated with irreversibly trapped ions in its structure [1]. In this report, effect of loading ratio of H.C and LTO composite anode on the electrochemical behavior of fast charging lithium ion battery is studied. Electrochemical characterization results show that a certain loading of H.C plays a critical role in improving the electrochemical performance of LTO-H.C composite electrodes. Specifically, superior cycling stability and specific capacity achieved for the composite electrode with 20 wt.% H.C. It is believed that composite electrodes with an optimized ratio can effectively contribute to Li-ion storage and form a robust protective solid electrolyte interface (SEI) on the electrode surface. The latter might minimize further electrolyte decomposition and continuous growth of the SEI layer upon cycling, then improves the cycling stability of the electrode. In addition, the cycling performance and rate capability of LiNiMnCoO2 (NMC) with different nickel (Ni) and manganese (Mn) contents were evaluated and compared. The results clearly suggest that higher Ni content can improve specific capacity (115 mAhg-1for NMC333 vs 149 mAhg-1 for NMC811 at 1C). However, cycling stability deteriorates with increasing the Ni content (77% capacity retention for NMC333 vs 45% for NMC811 after 300 cycles). It is postulated that electrodes with higher Ni content are susceptible to transition metal dissolution and side reactions at electrode-electrolyte interface, which could lead to performance degradation by impeding Li+ diffusion across the electrode, and irreversible consumption of Li+ [2]. Finally, the possibility of use of the optimized anode for fabricating full cell with the selected NMC cathode is investigated.

References:

[1] Weiss, M., Ruess, R., Kasnatscheew, J. et al. Fast Charging of Lithium‐Ion Batteries: A Review of Materials Aspects. Adv. Energy Mater 11,2101126 (2021).

[2] Lin, R., Bak, SM., Shin, Y. et al. Hierarchical nickel valence gradient stabilizes high-nickel content layered cathode materials. Nat Commun
12, 2350 (2021).
Improved Air Stability of Sulfide Electrolytes for All-Solid-State Li Batteries
Authors: Zhao Feipeng , Liang Jianwen , Sun Xueliang Andy
Published: July 2022

Sulfide-based solid electrolytes (SEs) are receiving increasing attention due to their high ionic conductivities (up to 10-2 S cm-1 at room temperature) that can be comparable to the liquid electrolytes.1 However, the air stability of sulfide SEs is very poor.2, 3 Most developed sulfide SEs are prone to turn bad when exposed to the moisture. The generated H2S is dangerous, which places the commercialization of sulfide SEs into a challenging situation. 2, 3

In our work, to improve the air stability of sulfide SEs, we employed element substitution (Sn and Sb) for the problematic element (P) in conventional sulfide SEs (Li3PS4, Li6PS5I, Li10GeP2S12) based on the hard and soft acid and base theory (HSAB).4, 5, 6 Our results suggest that Sn and Sb-substituted sulfide SEs show significantly improved air stability compared with the pristine sulfides. Meanwhile, it is found that the Sn or Sb element substitution effectively enhance the ionic conductivity as well as Li metal compatibility in some cases. Various structural (e.g., X-ray diffraction, X-ray absorption near edge spectroscopy, solid-state nuclear magnetic resonance) and electrochemical characterizations are employed to identify the mechanism of the improvements are related to the Sn/Sb substitution-derived crystal structure, reinforced bonding energy, and the optimized electrode/electrolyte interfaces. Our studies provide a new idea of designing functional sulfide composition to realize improved air stability coupling with other essential properties.

Re
ferences

N. Kamaya, R. Kanno*, et al. A lithium superionic conductor, Nat. Mater. 2011, 10, 682-686.

C. Yu, F. Zhao, J. Luo, X. Sun*. Recent Development of lithium argyrodite solid-state electrolytes for solid-state batteries: synthesis, structure, stability and dynamics. Nano Energy 2021, 83, 105858.

F. Zhao, S. Zhang, Y. Li*, X. Sun*. Emerging characterization techniques to understand electrode interfaces in all-solid-state lithium batteries. Small Struct. 2021, DOI: 10.1002/sstr.202100146.

F. Zhao, J. Liang, X. Sun*, et al. A Versatile Sn-Substituted Argyrodite Sulfide Electrolyte for All-Solid-State Li Metal Batteries, Adv. Energy Mater. 2020, 10, 1903422.

F. Zhao, X. Sun*, et al. An Air-Stable and Li-Metal-Compatible Glass-Ceramic Electrolyte enabling High-Performance All-Solid-State Li-Metal Batteries. Adv. Mater. 2021, 33, 2006577.

J. Liang, X. Sun*, et al. Li10Ge(P1–xSbx)2S12 Lithium-Ion Conductors with Enhanced Atmospheric Stability, Chem. Mater. 2020, 32, 2664-2672.
The Influence and Degradation Mechanism of the Depth of Discharge on the Performance of NMC-Based Cathodes for Li-Ion Batteries
Authors: Guo Jia , Li Yaqi , Pedersen Kjeld , Gurevich Leonid , Stroe Daniel-Ioan
Published: July 2022

Many factors affect the degradation behavior of lithium-ion (Li-ion) batteries and one of these is the depth of discharge (DOD). As Li-ion batteries are used, a reasonable DOD can not only extend their service life (by reducing the degradation rate) but can also reduce the frequency of the re-charging. Therefore, to investigate and clarify the effect of the DOD on cathode performance, we performed cycle aging tests on coin cells considering three DODs. Furthermore, we proposed a degradation mechanism, to account for the influence of the DOD on the cathode performance, through ex-situ post-mortem analysis.

The investigated positive electrode was from a commercial cathode NMC 532, assembled with a lithium metal anode in a 2016 type coin cell. The initial discharge capacity was about 163 mAh g–1 at a 1 C rate (1C taken as 160 mAh g–1). After every certain number of cycles, the 100% DOD (2.75 – 4.3 V) capacity was measured and recorded for all DOD ranges.

Our cycle aging test experiment results (in the below Figure) show that the capacity fades faster in the higher DOD range (i.e., 3.65 – 4.3 V); the capacity of coin cells showed an initial increase due to the initial activation and a rapid decline thereafter. In contrast, the battery capacity faded slower in the two lower DOD ranges (i.e., 2.75 – 4.3 V and 3.55 – 4.3 V). The results also show that the higher DOD makes the battery more active during the initial cycles, as shown in the Figure.

We refined and analyzed the XRD results of different states of the charged cathode to calculate the change in unit cell volume in initial different DOD cycles. By calculating the Li-ion diffusion coefficient through the EIS measurements, it was found that it is larger in the higher state of charge (SOC) state, which explains the higher activity of the cathode in a higher DOD range. Furthermore, we disassembled and analyzed the coin cells, after the same numbers of equivalent full cycles. Surface microcracks of the cathode were observed by SEM, and the cathode-electrolyte interphase (CEI) film was analyzed and quantified by XPS technology.

Based on these results, we concluded that higher DODs enable the material to maintain a faster Li-ion diffusion rate and are always in a highly activated state. At the same time, it leads to a faster cathode decay. The post-mortem analysis showed the detailed mechanism of degradation. Looking at the results of this study, frequent charging, making the battery operation at a higher voltage, aggravates deterioration of the cathode.

Acknowledgments

This project has received funding from the China Scholarship Council (no. 202006370035; no. 202006220024). Furthermore, the authors would like to thank Haidi company for providing the cathode material.

Figure 1
Difluorophosphoric Acid Generation and Crossover Reactions in LiNixCoyMnzO2 Cathodes
Authors: Jayawardana Chamithri , Lucht Brett L.
Published: July 2022

Layered LiNixCoyMnzO2 (NCM) materials are one of the most widely utilized cathode materials for Lithium-ion batteries (LIB) with their high theoretical capacity and relatively high voltage window. Increasing the Nickel content and the cycling voltage can increase the capacity of these cells at a lower cost. But these high Nickel cathodes cycled to a higher upper cut off voltage have poor cycling stability. The cause of this rapid capacity decrease has been attributed to decomposition of the anode solid electrolyte interphase (SEI) from transition metal deposition on the anode surface and impedance growth on the cathode surface. Recent studies have also attributed this to acidic species generated from oxidative decomposition of the electrolyte and their crossover reactions degrading the SEI, particularly the Difluorophosphoric acid.

In this study the role of transition metal dissolution and Difluorophosphoric acid generation has been investigated through various quantitative analysis techniques including, ICP-MS, XPS, quantitative solution NMR, and EIS. Full cells were constructed using graphite as the negative electrode and NCM cathodes with different Nickel contents as the positive electrode. These cells contain the same base electrolyte formulation (1.2M LiPF6 and EC: EMC, 3:7) and they were cycled at different temperatures and voltages to investigate the correlation between acid and transition metal concentration, cell voltage and capacity fade.
Surface Effects of Quench Methodology on Lithium Rich Nickel Manganese Oxide Cathode Particles
Authors: Burke Sven Anders , Whitacre Jay
Published: July 2022

Our investigation found that rapid cooling, through use of a water quench, of layered lithium rich nickel manganese oxide (LLRNMO) cathodes, post 900 °C calcination, resulted in cathode materials with significantly improved electrochemical performance and more homogenous physio-structural properties near the surfaces. Our investigation was conducted on LLRNMO from the Li[NixLi(1/3-2x/3)Mn(2/3-x/3)]O2 compositional series, where x = 0.25. Our material was prepared using a hybrid sol-gel route where the post 900 °C cooling step was varied between the two extremes, rapid quenching through water immersion (sample Wq), and slow natural oven cooling (sample Oc). Surface analysis of these samples was conducted before and after repeated galvanostatic-static constant-current potential limited (GCPL) cycling of coin cells with cathodes made of these active materials to elucidate any electrochemical effects that could arise from the physio-structural differences between the samples. Surface analysis was conducted using high resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy (STEM), energy dispersive spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). The rapidly quenched Wq samples were found to have higher specific capacities, higher average discharge voltages, greater cycle stability, and greater voltage stability when compared to the Oc samples. This is consistent with one of our previous investigations.1 Surface studies of the samples revealed that the pristine Oc samples had evidence of phase segregation between the nickel poor bulk phase and a nickel rich surface phase. These two phases were reminiscent of a core/shell architecture. Surface analysis conducted after the course of cycling suggested that the concentration of transition metals homogenized over the course of cycling, resulting in less distinction between the surface and bulk phases, as well as the nucleation of defect phases. These behaviors of the Oc samples are in large contrast to the Wq samples’ where the surface and bulk phases were isostructural with more homogenous concentrations of transition metals. These data suggest that more rapidly quenched samples see increased stabilization of the meta-stable R-3m phase resulting in the reported superior electrochemical properties.

S. Burke and J. F. Whitacre, J. Electrochem. Soc., 167, 160518 (2020).

Figure 1
Aryl Diazonium- and Pyrene-Functionalised Graphite for Lithium-Ion Batteries
Authors: Bauer Marina , Pfeifer Kristina , Radinger Hannes , Luo Xianlin , Konnerth Philipp , Bauer Felix , Scheiba Frieder
Published: July 2022

One of the main reasons for battery aging in lithium-ion batteries (LIBs) is the formation of a solid electrolyte interphase (SEI). SEI formation results in capacity loss and power fading due to irreversible electrochemical decomposition of electrolyte. However, the SEI protects the negative electrode from further parasitic surface reactions with the electrolyte. Therefore, it is of great interest to learn more about factors influencing the SEI and its formation. One approach is to modify the surface of the active material.

Since graphite is commonly used as negative electrode material in LIBs, we modified graphite with anchor molecules featuring functional groups. In particular, we use aryl diazonium salts and pyrenes as anchor molecules to cover a covalent and a non-covalent approach. The influence of different functional groups on the electrochemical properties of graphite electrodes is investigated. Furthermore, the importance of the modification method and the influence of the anchor molecule is addressed. The functional groups of modified graphite electrodes enable further layer growth, which is an important aspect for the design of an artificial SEI.

For surface and electrochemical characterisation of the modified graphite samples, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and galvanostatic cycling are used.

Financial support of the German Research Foundation (DFG) within the project B2 of the Collaborative Research Centre (SFB 1176) is kindly acknowledged.
Measurement of Internal Stresses Exerted in an Each Layer of Multiple Layer's Film with Temperature Using a Grazing Incidence X-Ray Diffraction
Authors: Takayama Shinji
Published: July 2022

The internal stresses in an each layer of multiple layer's film (AZO, Cu, and Mo) has been measured experimentally using grazing incidence X-ray diffraction. This was performed utilizing the difference of total reflection values between consisting layers so as to be able to measure the each internal stresses in turn by the GISD.
(Invited, Digital Presentation) Driven Nucleation and Growth in Lithium Batteries
Authors: Bazant Martin
Published: July 2022

This talk will describe the physics of driven nucleation and growth in battery materials. The resulting nonequilibrium pattern formation may be either reaction-limited or transport limited. Examples of the former include driven phase separation in Li-ion batteries, electrodeposition in Li-air batteries, and Li plating in Li-ion batteries, controlled by electro-autocatalysis and competing electrochemical reactions. Examples of the latter include stable electrodeposition in Li-metal batteries with charged porous separators, controlled by deionization shock waves.
(Invited) Elucidating Solvation Structures and Their Impact on SEI Formation at Electrode-Electrolyte Interfaces
Authors: Zhang Yingjie
Published: July 2022

Solvation layers, also called electric double layers (EDLs), crucially modulate all the electrochemical processes at electrode-electrolyte interfaces, and serve as "precursors" for the nucleation and growth of interphasial species. However, the molecular structure of EDLs remains largely elusive. In this talk, I will discuss our recent efforts on characterizing the EDL structure via scanning probe microscopy and vibrational spectroscopy. Furthermore, I will show our efforts on imaging the nucleation and growth processes of solid-electrolyte interphases (SEIs) on graphite electrodes. In the end, I will discuss about the correlation between EDL and SEI, and the implications on the design of battery electrolytes.
(Invited) Atom Probe Tomography: A New Tool For the Analysis of Solid Liquid Interfaces?
Authors: Schmitz Guido
Published: July 2022

Atom probe tomography is an established method for the microsocopic analysis of hard materials, which stands out by combining single-atom sensitivity with a 3D volume reconstruction. The method is based on laser-assisted field evaporation from nanometric emitter tips. In solid state reactions it delivered decisive information to understand the detailed conditions of nucleation and growth of product phases. In recent efforts, we desire to break the materials limitations aiming for application to liquids, softmatter and polymeric materials. To this end, a new instrument has been constructed that joins cryogenic ion beam preparation with a flexible transfer into an atom probe chamber. Meanwhile, we are able to produce nanometric needles from frozen liquids, even from pure water [1]. Studies are performed with aqueous solutions [2], liquids of short alkanes [3], self-assembling monolayers [4]. The talk discusses the field desorption of complex materials and presents time of flight mass spectra and their dependence on field or laser intensity. The complex mechanisms of field desorption from frozen water surfaces are further elucidated by DFT and Monte-Carlo simulation. Finally, by evaluating evaporation probabilities and event correlations, even insight in bonding strength and the stability of molecules in strong electrical fields may be provided.

[1] T. M. Schwarz, E. M. Weikum, K. Meng, E. Hadjixenophontos, C. A. Dietrich, J. Kästner, P. Stender, G. Schmitz, Field evaporation and atom probe tomography of pure water tips, Nature Scientific Reports (2020) 10:20271 | (DOI: 10.1038/s41598-020-77130-x

[2] T. M. Schwarz, C. A. Dietrich, J. Ott, E. M. Weikum, R. Lawitzki, H. Solodenko, E. Hadjixenophontos, B. Gault, J. Kästner, G. Schmitz, P. Stender, 3D Sub-Nanometer Analysis of Glucose in an Aqueous Solution by Cryo-Atom Probe Tomography, Scientific reports 11 (2021) 11607 (DOI: 10.1038/s41598-021-90862-8)

[3] Kuan Meng, Tim Schwarz, Eric Weikum, Patrick Stender, Guido Schmitz, Frozen n-Tetradecane investigated by cryo-Atom Probe Tomography, J. Microsc. Microanal. (2021), 1-11; (DOI:10.1017/S14319276210125)

[4] Helena Solodenko, Patrick Stender, Guido Schmitz, “Atom Probe Study of 1-octadecanethiol self-assembled Monolayers on Platinum (111) and (200) surfaces”, J. Microsc. Microanal. (2021), 1–10. (DOI: 10.1017/S1431927621012654)
Platinum Catalyst Degradation: Unusual Nucleation and Growth of Nanoislands
Authors: Valls Mascaró Francesc , Koper Marc T. M. , Rost Marcel J.
Published: July 2022

The longevity of a catalyst plays a crucial role for many industrial scale applications. Platinum is the best candidate to be used in electrochemical energy conversion systems due to its high activity. However, platinum catalysts degrade during fuel cell operation. The origin of this degradation, the loss of material, is very likely rooted in the roughening of the surface: the nucleation and growth of nanoislands [1, 2, 3, 4]. It is known that the extend of this roughening can be tuned by additives, change of the electrolyte pH, or operation within different potential windows [5, 6, 7]. In this work, we study the degradation of different platinum stepped surfaces under potential cycling to oxidative potentials. Interestingly, we quantify significantly less degradation on surfaces with narrower terraces: Ra(Pt(111)) > Ra(Pt(15 15 14)) > Ra(Pt(554)) > Ra(Pt(553)) > Ra(Pt(533)). We present here a model that explains this trend, in which steps act like sinks for both adatoms and vacancies, slowing down the nucleation and growth of the above mentioned nanoislands. We support our results, which were derived until now solely on electrochemical measurements, with in-operando Electrochemical Scanning Tunneling Microscopy (EC-STM) images.

References:

[1] Jacobse, L. et al., Nat. Mater. 17, 277 (2018)

[2] Jacobse, L. et al., ACS Cent. Sci. 5 (12), 1920 (2019)

[3] Rost, M.J. et al., Nat. Commun. 10, 5233 (2019)

[4] Hanselman, S. et al., Phys. Chem. Chem. Phys. 22, 10634 (2019)

[5] Lopes, P.P. et al., ACS Catal. 6, 2536 (2016)

[6] Topalov, A. et al., Chem. Sci., 5, 631 (2014)

[7] Ruge, M. et al., J. Am. Chem. Soc., 139, 4532 (2017)
Thick Copper Layer Growth By Dynamic Hydrogen Bubble Template Using Continuous and Pulse Currents
Authors: Schoenleber Jonathan , Gigandet Marie-Pierre , Fedi Baptiste , Hihn Jean-Yves
Published: July 2022

Copper is the most widely used materials for microelectronics applications due to their electrical and thermal conduction properties, and in several appplications, thick and porous layers are requested.

Different possibilities still exists such as copper-zinc or copper-manganese electrodeposition followed by an anodic dissolution, but the faster and simpler way resides in electroforming deposition made by Dynamic Hydrogen Bubble Template (DHBT) [1]. This process works in unusual potentials and current densities where the competition between hydrogen discharge (commonly avoided) and copper reduction is very high. In this case, this method achieves thick deposits in very short time (few seconds) with high currents allowing a very fast growth of copper around hydrogen bubbles. Pores and ligaments sizes can be controlled by several operating parameters i.e. current densities, temperature, deposit time as well as by chemical additives [2].

With the use of a copper sulphate acid bath at various concentrations, with or without additives (acetic or hydrochloric acids) and by applying current densities between 100 and 400 A.dm-2, it is possible to obtain thick and porous coatings, with pores diameters between 10 and 500 µm and ligaments length between 10 and 200 µm. An example of a SEM image shows the morphology of the deposits obtained in top view and in cross section (Figure 1). Another possibility to control the 3D growth resides in the use of pulsed currents, with an effect on bubbles size. Furthermore, reverse pulses are useful for edge effects limitation.

[1] Abdel-Karim, R.; El-Raghy, S. Chap 4 in Advanced materials and their applications - micro to nano scale. One Central Press, United Kingdom, pp 69–91, 2017

[2] Shin, H.-C.; Liu, M. Chem. Mater. 2004, 16, 25, 5460–5464 doi.org/10.1021/cm048887b

Figure 1 : SEM images of a) top view and b) cross section of a DHBT copper deposit

Figure 1
(Invited) Quantitatively Designing Porous Copper Current Collectors for Lithium Metal Anodes
Authors: Meng Shirley
Published: July 2022

Lithium metal has been an attractive candidate as a next-generation anode material. Despite its popularity, stability issues of lithium in the liquid electrolyte and the formation of lithium whiskers have kept it from practical use. Three-dimensional (3D) current collectors have been proposed as an effective method to mitigate whiskers growth. Although extensive research has been done, the effects of three key parameters of the 3D current collectors, namely the surface area, the tortuosity factor, and the surface chemistry, on the performance of lithium metal batteries remain elusive. Herein, we quantitatively studied the role of these three parameters by synthesizing four types of porous copper networks with different sizes of well-structured micro-channels. X-ray microscale computed tomography (micro-CT) allowed us to assess the surface area, the pore size and the tortuosity factor of the porous copper materials. A metallic Zn coating was also applied to study the influence of surface chemistry on the performance of the 3D current collectors. The effects of these parameters on the performance were studied in detail through Scanning Electron Microscopy (SEM) and Titration Gas Chromatography (TGC). Stochastic simulations further allowed us to interpret the role of the tortuosity factor in lithiation. The optimal range of the key parameters is thereby found for the porous coppers and their performance is predicted. Using these parameters to inform the design of porous copper anodes for Li deposition, Coulombic efficiencies (CE) of up to 99.63% are achieved, thus paving the way for the design of effective 3D current collector systems.
(Invited) 3-D Visualization of Li Metal Plating and Stripping with Operando Video Microscopy
Authors: Dasgupta Neil P.
Published: July 2022

In recent years, there has been an explosion of research into Li metal anodes for high-energy-density batteries. However, despite tremendous progress in the field, the reversible plating and stripping of Li has been hindered by the complex interplay between electrode morphology, surface chemistry, and mechanics. This has led to many empirical observations of improved performance, but our ability to rationally design solutions to solve the challenges of reversibility remain limited by our fundamental understanding of the complex electrodeposition and dissolution processes involved [1]. In an analogous example, Li plating on graphite anodes during fast-charging also plagues the Li-ion community [2], but fundamental studies of the complex nature of Li plating on intercalation electrodes is equally lacking.

To address these challenges, in situ/operando analyses are of paramount importance to the community. However, given the dynamic nature of Li plating and stripping, challenges arise with respect to tradeoffs in spatial and temporal resolution. To address these challenges, we have recently integrated our optical visualization cells with a digital microscope capable of focus variation microscopy. This enables 3-D visualization of the electrode morphology with high temporal resolution, allowing for video capture of Li plating and stripping [2-3].

In this talk, I will discuss the application of operando 3-D microscopy for visualization of both Li metal anodes and Li plating on graphite surfaces during fast-charging of Li-ion batteries. In the case of Li metal anodes, we observe significant anisotropy in the geometric shape of individual pits during stripping [3]. The nucleation density and anisotropy are shown to be strongly influenced by the surface microstructure and underlying crystallographic texture of the Li metal surface. As a results, pits can exhibit strong faceting, which influences the nature of nucleation at pit edges in subsequent cycles [4]. As a parallel example, we demonstrate 3-D visualization of Li plating on graphite electrodes during fast-charge, which illustrates the coupling between nucleation of Li plating and local heterogeneity in state-of-charge [2]. Overall, these results highlight the importance of both spatial and temporal heterogeneity in the nature of nucleation, growth, dissolution, pitting, and dead Li formation

References

[1] K. N. Wood, M. Noked, N. P. Dasgupta, ACS Energy Lett.
2, 664 (2017).

[2] Y. Chen, K.-H. Chen, A. J. Sanchez, E. Kazyak, V. Goel, Y. Gorlin, J. Christensen, K. Thornton, N. P. Dasgupta, J. Mater Chem. A
9, 23522 (2021).

[3] A. J. Sanchez, E. Kazyak, Y. Chen, J. Lasso, N. P. Dasgupta, J. Mater Chem. A.
9, 21013 (2021).

[4] A. J. Sanchez, E. Kazyak, Y. Chen, K.-H. Chen, E. R. Pattison, N. P. Dasgupta,
ACS Energy Lett.
5, 994 (2020).
Bottom-up Gold Filling for Manufacture of X-Ray Gratings: To What Limit?
Authors: Josell Daniel , Moffat Thomas P
Published: July 2022

Since its discovery three years ago, a process enabling extreme superconformal deposition of gold in recessed features has been advanced to achieve void-free filling of progressively more varied and challenging features and patterned substrates for application in X-ray imaging. During the past year in particular, void-free filling in vias, trenches with aspect ratio (height/width) exceeding 60, trenches more than 300 mm deep, fractal patterns of spatially varying depth and fully patterned 100 mm wafers for all the aforementioned were demonstrated for the first time. Examples are shown in the included figure. The process and mechanism differ substantially from processes for superconformal copper filling of nanometer size damascene on-chip trenches and vias as well as micrometer size through silicon vias and even larger microvias used to connect semiconductor chips in the microelectronics industry. The bottom-up deposition can be initiated using a wide range of processing conditions so that filling is robust even to process interruption including wafer removal and rinse. Because the bottom-up evolution can also be made to self-passivate at a chosen depth below feature openings well controlled fill profiles can be obtained across wafer scale substrates, even with features of variable width and depth. I present examples of the noted feature filling results with relevant electrochemistry and discuss aspects of the deposition processes and underlying mechanism.

Figure 1
Diversity Matters: Influence of Surface Heterogeneities in the Electrochemical Nucleation and Dissolution of Au Nanoparticles
Authors: Bernal Lopez Miguel , Torres Daniel , Semsari Parapari Sorour , Čeh Miran , Žužek Rožman Kristina , Šturm Sašo , Ustarroz Jon
Published: July 2022

The investigation of the nucleation and dissolution of gold nanoparticles on a glassy carbon substrate with Scanning Electrochemical Cell Microscopy (SECCM) combined with in-situ electrochemical TEM (EC-TEM) revealed the subtle influence of the local properties of the substrate on the electrochemical processes. Conducting hundreds of locally-resolved voltammograms at the micro-scale resulted in the observation of a diversity of responses for nucleation, allowing to address experimentally the statistical nature of the nucleation and growth process. Moreover, during the electrochemical dissolution of previously electrodeposited nanoparticles (NPs), the confinement conditions of the SECCM-cell allowed the resolution of a multitude of events characterized as current spikes. Such current events are not observable in the macro-scale since the electrochemical response over the large electrode area is the convolution of the activity all over the electrode surface. The EC-TEM experiments demonstrated that such current spikes were generated by the dissolution of individual NPs distributed over a time range. Combining SECCM and EC-TEM unmasked information previously not seen from the electrochemical nucleation, growth, and dissolution of supported metal nanoparticles [1]. This approach could accelerate the discovery of novel functional electrode materials by facilitating the rational design of protocols for electrodeposition of nanostructured materials and the evaluation of their stability under electrochemical conditions. The possibility to consider the heterogeneous nature of the supports and the differences within nanomaterial ensembles opens the opportunity to consider the diversity of electrochemical parameters as descriptors to understand and describe the relationships between activity, stability, and structure.

[1] M. Bernal, D. Torres, S. Semsari, M. Čeh, K. Žužek Rožman, S. Šturm, J. Ustarroz, Diversity matters: Influence of surface heterogeneities in the electrochemical nucleation and dissolution of Au nanoparticles, under revision
(Digital Presentation) On Epitaxial Electrodeposition of Co, Ru and Cu for Interconnect Applications
Authors: Barmak Katayun
Published: July 2022

As the critical dimensions of copper (Cu) interconnects approach dimensions near the mean free path of the metal (39.9 nm at room temperature), a rise in resistivity is observed. This phenomenon, termed resistivity size-effect, is the result of electron scattering at grain boundaries and surfaces. Given that electron scattering from grain boundaries is a major contributor to the resistivity rise in nanoscale interconnects, in this study we demonstrate epitaxial electrodeposition of single crystal and bicrystal films, using Co, Ru and Cu as three metals of choice. In detail, we will address the choice of seed layer, the role of symmetry of the seed layer, the sign and magnitude of the misfit strain (compressive, none, tensile), the epitaxial orientation relationship of the electrodeposited film and the seed layer, the impact of underpotential deposition on film nucleation, and the growth morphology. The role of electrolyte, ion concentration and pH will also be addressed.
(Invited) Effect of Additive Species on the Nucleation and Growth Process on Zn Negative Electrode Surface
Authors: Homma Takayuki , Onabuta Yusuke , Otani Tomohiro , Kunimoto Masahiro , Fukunaka Yasuhiro
Published: July 2022

Zn is one of the promising candidates as negative electrode materials for next-generation secondary batteries, especially those for large capacity applications such as grid-scale energy storage. While the Zn has numbers of attracting features such as crustal abundance, applicability of aqueous system, etc., which enable to realize the secondary batteries with high performance and safety with lower cost, the major drawback is evolution of irregular morphology called mossy structure with highly filamentous features at the electrode surface during charge-discharge cycles. Unlike the conventional dendritic growth which proceeds under diffusion-limited conditions, formation of the mossy structure takes place without such a condition. At the same time, it has been reported that the growth of these irregular structures could be suppressed by applying metallic species as additives to form uniform electrodeposition [1]. We have investigated formation process of the mossy structure on the Zn anode surface, focusing on its initial stage in combination with the additive effects such as Pb and Sn [2]. In this presentation, we will introduce the results of our research on the nucleation and growth process of the mossy structure through experimental analysis and computational modeling. For the theoretical calculation, we attempted to develop multi-scale simulation model by employing density functional theory (DFT) and kinetic Monte Carlo (KMC) approaches [3], and the results will be described focusing on the effects of the metallic additives.

This work is financially supported in part by MEXT/JSPS Grant-in-Aid for Scientific Research No. 21H01642.

[1] For example, F. Mansfeld, S. Gilman, J. Electrochem. Soc. 117, 1328 (1970); Y. Ito, M. Nyce, R. Plivelich, M. Klein, D. Steingart, S. Banerjee, J. Power Sources, 196, 2340 (2011).

[2] For example, T. Otani, M. Nagata, Y. Fukunaka, T. Homma, Electrochim. Acta, 206, 366 (2016); T. Otani, Y. Fukunaka, T. Homma, Electrochim. Acta, 242, 364 (2017).

[3] Y. Onabuta, M. Kunimoto, S. Wang, Y. Fukunaka, H. Nakai, T. Homma, J. Phys. Chem.C, submitted.
(Digital Presentation) Mechanistic Understanding of Rhenium Electrodeposition
Authors: McBride Michael , Dervishi Enkeleda , Edwards Randy , Stull Jamie A , Clark Courtney L , Hooks Daniel E
Published: July 2022

The electrodeposition of rhenium (Re) has received renewed attention in the past decade for a wide range of applications in aerospace, nuclear, catalysis, biomedical and electrical fields. Rhenium has unique and superior properties when compared with other refractory metals, making it attractive as an engineering material. It has a very high modulus of elasticity and superior tensile strength and creep-rupture strength over a wide temperature range. Re also is very resistant to highly corrosive environments, possesses a very high melting point, and enhanced wear resistance properties. However, Re is difficult to deposit by electrolysis of their aqueous solutions due to its very low over potential for hydrogen evolution.

The electrodeposition of rhenium has been demonstrated in the literature with approaches ranging from simple acidic solutions, induced codepostion with iron group metals, and water-in-salt electrolytes. However, these coatings are generally deposited at low Faradaic efficiency, are brittle, and limited in the obtainable thickness (sub-micron) due to absorbed hydrogen and formation of oxide phases.

Herein, we present systematic studies progressing towards the development of stable and efficient electrolytes to enable the electrodeposition of thick (100+ microns) Re coatings. Examples from both simple acidic solutions and water-in-salt electrolytes will be presented. Specifically, we correlate nucleation and growth mechanisms of Re with the ability to produce thick coatings. Pulse/pulse reverse electroplating was applied to manipulate the obtained grain structure. Correlations between electrolyte composition and pulse parameters with observed morphology will be discussed.

The ultimate goal of this project is the electrodeposition of rhenium-cobalt (Re-Co) graded density samples of millimeter thickness. Thus, understanding how to transition from a coating of pure metallic rhenium to a graded composition of Re-Co as a function of dynamic processing conditions will be presented. Towards this end, we are using a combination of electrochemical techniques with in situ measurements (atomic force microscopy, Raman, optical microscopy) to isolate variables controlling nucleation and growth which lead to the grain structure of the deposit.

LA-UR-21-31694
Elucidating and Mitigating High-Voltage Interfacial Chemomechanical Degradation of Nickel-Rich Lithium-Ion Battery Cathodes Via Conformal Graphene Coating
Authors: Luu Norman , Lim Jin-Myoung , Torres Castanedo Carlos Gerardo , Park Kyu-Young , Moazzen Elahe , He Kun , Meza Patricia E. , Li Wenyun , Downing Julia , Hu Xiaobing , Dravid Vinayak , Barnett Scott A , Bedzyk Michael , Hersam Mark C
Published: July 2022

Layered-type, nickel-rich lithium nickel manganese cobalt oxides (NMCs) are well-established cathode materials for high-performance lithium-ion batteries. These materials exhibit stable cycling within mild voltage windows (up to 4.3 V vs. Li/Li+) but can be charged to higher potentials (4.8 V vs. Li/Li+) to access additional capacity. However, high-voltage operation is generally avoided due to severe interfacial and chemomechanical degradation, such as electrolyte decomposition reactions and non-uniform buildup of chemomechanical strains that can result in particle fracture and compromised cyclability.

In this work, we find that a conformal graphene coating enables significant enhancements in the cycle life and coulombic efficiency of NMC cathodes during high voltage electrochemical cycling. Postmortem surface chemical analysis reveals that graphene-coated NMC electrodes exhibit reduced spectral intensities corresponding to electrolyte decomposition products, suggesting that the interfacial graphene layer limits parasitic electrode-electrolyte interactions. Furthermore, global and local structural analysis shows that the graphene coating mitigates mechanical degradation, which was evidenced by reduced microstrain, particle fracture, and electrochemical creep. Based on these observations, we propose a mechanistic relationship between the spatial uniformity of lithium flux and primary particle-level mechanical degradation, and show that a conformal graphene coating is well-suited to address these issues associated with high voltage chemomechanical degradation. Overall, these results delineate a pathway for rationally mitigating high-voltage chemomechanical degradation of nickel-rich cathodes that can be applied to existing and emerging classes of battery materials.

https://doi.org/10.1021/acsaem.1c01995
In Operando Diffraction Radiography and Tomography on Li-Ion Batteries
Authors: Schoekel Alexander , Baran Volodymyr , Senyshyn Anatoliy
Published: July 2022

Diffraction radiography and tomography were used to study different commercial Li-ion batteries. Depending on the data processing either 'direct' parameters, such as phase distributions, or more abstract, derived parameters, like degree of lithiation of the graphite anode or even local state of charge, can be extracted. Especially the lithium distribution is an interesting parameter and is surprisingly inhomogeneous throughout the volume of a commercial battery cell.
Polysiloxane-Based Single-Ion Conducting Polymer Electrolyte for High-Performance Li‖NMC811 Batteries
Authors: Liang Hai-Peng , Zarrabeitia Maider , Chen Zhen , Jovanovic Sven , Merz Steffen , Granwehr Josef , Passerini Stefano , Bresser Dominic
Published: July 2022

The ongoing electrification of the transportation sector is triggering a continuous search for batteries with higher energy density. One approach to achieve this goal is the transition to lithium-metal anodes. However, the practical implementation brings about severe safety issues such as the dendritic deposition and growth of metallic lithium and the consequent risk of accidental short circuiting of the cell, resulting in a thermal runaway.1 Solid-state electrolytes such as polymers are considered a viable strategy to overcome this issue, especially single-ion conducting polymers, owing to the absence of the detrimental reversed cell polarization, the uniform Li+ flux, and frequently higher limiting current densities.2,3 In fact, the latter is of utmost importance for the fast charging of battery cells as well as the eventual power density. So far, however, the cycling performance at high dis-/charge rates and high current densities for battery cells comprising a polymer electrolyte remained little investigated and commonly non-satisfactory.

Here, we report the development of a polysiloxane-based single-ion conducting polymer electrolyte (PSiOM) with a Li+ conductivity exceeding 10−4 S cm−1 at ambient temperature and excellent stability towards both lithium metal and high-energy LiNi0.8Co0.1Mn0.1O2 (NMC811) as the active material for the positive electrode. This new polymer electrolyte enables dendrite-free lithium deposition, thanks to the formation of a suitable electrode|electrolyte interface and interphase and the uniform Li+ flux. Moreover, PSiOM allows for an outstanding capacity retention of, e.g., 90% at 1C and 86% at 2C after 300 cycles and rapid charging and discharging at C rates as high as 5C. It is important to note that we used reasonable active material mass loadings for these tests (>7 mg cm-2), which means that the current densities applied were up to 7.20 mA cm−2 at 40 °C and 2.88 mA cm−2 at 20 °C. To the best of our knowledge, these current densities are among the highest reported so far for polymer-based electrolytes.

References

(1) Kalhoff, J.; Eshetu, G. G.; Bresser, D.; Passerini, S. Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives. ChemSusChem
2015, 8 (13), 2154–2175.

(2) Zhang, H.; Li, C.; Piszcz, M.; Coya, E.; Rojo, T.; Rodriguez-Martinez, L. M.; Armand, M.; Zhou, Z. Single Lithium-Ion Conducting Solid Polymer Electrolytes: Advances and Perspectives. Chemical Society Reviews
2017, 46 (3), 797–815.

(3) Nguyen, H.-D.; Kim, G.-T.; Shi, J.; Paillard, E.; Judeinstein, P.; Lyonnard, S.; Bresser, D.; Iojoiu, C. Nanostructured Multi-Block Copolymer Single-Ion Conductors for Safer High-Performance Lithium Batteries. Energy & Environmental Science
2018, 11 (11), 3298–3309.
Lithiation-Driven Crystallization of Ni-Based Cathode Materials during Calcination
Authors: Liu Sizhan , Chen Ke , Kahvecioglu Ozgenur , Bai Jianming , Wang Feng
Published: July 2022

Driven by the increasing need of energy storage for electric vehicles and electronic devices, the technological advancements of lithium-ion batteries (LIBs) are urgently in demand to increase energy density while reducing cost. LiNixMnyCo1-x-yO2 (NMC) is among the most promising low-cost, high-energy-density cathodes for next-generation LIBs.[i]
,[ii]
NMC cathode materials are generally synthesized through high-temperature calcination of NMC and lithium hydroxides. Control of the calcination conditions has been found crucial to obtaining high-performance NMC cathodes, wherein structural ordering and morphology of the final products are finely tuned to maximize capacity while minimizing surface areas exposed to the electrolyte.[iii]
,[iv]
However, making NMC cathode materials of desired structural properties has been challenging due to the complexity of the calcination process, involving phase transformation accompanied with non-equilibrium crystallization of intermediates prior to forming the layered oxides.[v]
,[vi]

In this work, a combination of in situ X-ray spectroscopy and microscopy techniques is applied to track the calcination process during synthesis of the practical system LiNi0.8Mn0.1Co0.1O2 (NMC811) and the archetypal LiNiO2 (LNO). The reaction pathways and structural evolution of the involved phases were identified, revealing the strong compositional dependence of phase progression, structural ordering, and crystal growth during the calcination process. A strong correlation was found between the degree of lithiation in the rocksalt phase and the progression of the layered phase (see figure 1). In NMC811, the lithiation is facilitated by Co/Mn leading to the highly lithiated rocksalt and resulting in rapid layering at low temperatures. The nucleation of the layered phase is predominately driven by lithiation, while the growth process is kinetically limited by the sluggish Ni diffusion in LNO and further hindered in NMC811 due to the presence of Co/Mn. The findings from this study, with insights into crystallization thermodynamics and kinetics, may provide guidance to the design and synthesis of high-performance Ni-based NMC cathode materials.

[i] N. Nitta, F. Wu, J. T. Lee, and G. Yushin, Materials today, 2015, 18(5), 252-264.

[ii] M. S. Whittingham, Chemical reviews, 2014, 114(23), 11414-11443.

[iii] J. C. Garcia, J. Bareño, J. Yan, G. Chen, A. Hauser, J. R. Croy, H. Iddir, The Journal of Physical Chemistry C, 2017, 121(15), 8290-8299.

[iv] Y. Duan, L. Yang, M. J. Zhang, Z. Chen, J. Bai, K. Amine, F. Pan, F. Wang, Journal of Materials Chemistry A, 2019, 7(2), 513-519.

[v] M. Bianchini, F. Fauth, P. Hartmann, T. Brezesinski, J. Janek, Journal of materials Chemistry A, 2020, 8(4), 1808-1820.

[vi] F. Wang, J. Bai, Batteries & Supercaps, 2021. (https://doi.org/10.1002/batt.202100174)

Figure 1