Cobalt-free cathodes and silicon thin-film anodes towards high-capacity solid-state batteries
Not Available
25 ENERGY STORAGE↗
Engineering topics
Lee, Steven
Publications and source records attributed to Lee, Steven.
Mixed ionic-electronic conductivity of high-nickel, single-crystal cathodes influencing the cycling stability of all-solid-state lithium-ion batteries
Removing cobalt lowers the electronic conductivity of high-nickel cathodes. A mismatch between electronic and ionic conductivities in the cathode composite leads to reaction inhomogeneity and peculiar cycling behavior in all-solid-state batteries.
Lee, Steven↗
Cost‐Effective Layered Oxide – Olivine Blend Cathodes for High‐Rate Pulse Power Lithium‐Ion Batteries
Abstract Sustainability and supply‐chain concerns require lithium‐ion batteries (LIBs) free from critical minerals, such as nickel and cobalt. While recent advances provide encouraging signs that cobalt can be removed, the question remains how much Ni can be removed from Co‐free layered oxide cathodes before sacrificing critical performance metrics. This study highlights the effect of reducing Ni by benchmarking several Co‐free cathodes with decreasing Ni content. Keeping the energy density the same by increasing the charge voltage, cathodes below 80% Ni content exhibit worsened capacity fade due to increasing oxygen release and electrolyte decomposition. Charge transfer and diffusion kinetics are also hindered with increasing Mn content and exacerbated by resistive surface phases formed at high voltages, rendering lower‐Ni, Co‐free cathodes less competitive than high‐Ni cathodes for high energy and power applications. It is demonstrated blending layered oxide with olivine as an effective alternative to deliver energy density and cycling stability comparable to lower‐Ni cathodes with moderate charging voltages. Blending with 30 wt% olivine LiMn 0.5 Fe 0.5 PO 4 (LMFP) virtually eliminates the diffusion limitation of layered oxides at low state‐of‐charge, with enhanced pulse power characteristics rivaling the high‐Ni counterparts. Cathode blending can further reduce the overall Ni content and cost without the performance limitations of lower‐Ni, Co‐free cathodes.
Lee, Steven↗
Effects of Calcination Conditions on the Structural and Electrochemical Behaviors of High‐Nickel, Cobalt‐Free LiNi 0.9 Mn 0.1 O 2 Cathode
Abstract Eliminating cobalt from high‐nickel layered oxide cathodes lowers the cost of lithium‐ion batteries for electric vehicles. However, cobalt‐free cathodes with high Mn 4+ and Ni 2+ contents are prone to Li/Ni mixing after synthesis, potentially compromising battery energy density, rate capability, and cycling stability. Without cobalt facilitating cation ordering in the layered structure, the degree of Li/Ni mixing in cobalt‐free cathodes depends heavily on the calcination conditions. In this study, a systematic exploration of calcination temperatures and LiOH ratio for LiNi 0.9 Mn 0.1 O 2 (NM‐90) provides detailed insights into the optimal synthesis conditions for high‐capacity cobalt‐free cathodes with extended cycle life. Surprisingly, high Li/Ni mixing does not necessarily lead to poor cycling stability whereas low Li/Ni mixing does not guarantee a long cycle life. More importantly, although excessive calcination temperature can further decrease Li/Ni mixing, it does not necessarily enhance capacity. Instead, the pernicious effects from the H2 → H3 phase transition are amplified due to a pronounced two‐phase reaction. An extensive suite of chemical and structural characterization methods uncovers a correlation between elevated calcination temperature, phase transformation, cation ordering, and capacity fading behavior: “overcooking” high‐nickel, cobalt‐free cathodes induce structural arrangement toward that of LiNiO 2 , with exacerbated lattice distortion and surface instability accelerating capacity fade.
Lee, Steven↗
Cracking vs. surface reactivity in high-nickel cathodes for lithium-ion batteries
High-nickel layered oxide cathodes LiNi x Mn y Co z O 2 (NMC) experience microcracks during cycling. This can expose fresh cathode surfaces for parasitic reactions and isolate active cathode material from the conductive electrode matrix, resulting in impedance increase and capacity fade. The commonly held belief attributes microcracks to anisotropic lattice volume changes of primary particles during cycling. Nevertheless, recent reports suggest that certain electrolytes might reduce microcracks in NMC cathodes during deep cycling. This raises a crucial question on the origin of microcracks: do microcracks exacerbate surface stability, or does poor surface stability contribute to microcrack formation? This perspective aims to provide context and expound this “chicken or egg” dilemma. We contend that the consequence of surface reactivity on the cycle life of high-Ni cathodes is more pronounced than that of particle cracking. Here, we hypothesize that particle cracking is more of a symptom of severe surface reactivity rather than a cause of capacity fade.
25 ENERGY STORAGE↗
The DAMIC-M experiment: Status and first results
The DAMIC-M (DArk Matter In CCDs at Modane) experiment employs thick, fully depleted silicon charged-coupled devices (CCDs) to search for dark matter particles with a target exposure of 1 kg-year. A novel skipper readout implemented in the CCDs provides single electron resolution through multiple non-destructive measurements of the individual pixel charge, pushing the detection threshold to the eV-scale. DAMIC-M will advance by several orders of magnitude the exploration of the dark matter particle hypothesis, in particular of candidates pertaining to the so-called “hidden sector.” A prototype, the Low Background Chamber (LBC), with 20g of low background Skipper CCDs, has been recently installed at Laboratoire Souterrain de Modane and is currently taking data. We will report the status of the DAMIC-M experiment and first results obtained with LBC commissioning data.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Can Cobalt Be Eliminated from Lithium-Ion Batteries?
Following the discovery of LiCoO 2 (LCO) as a cathode in the 1980s, layered oxides have enabled lithium-ion batteries (LIBs) to power portable electronic devices that sparked the digital revolution of the 21st century. Since then, LiNi x Mn y Co z O 2 (NMC) and LiNi x Co y Al z O 2 (NCA) have emerged as the leading cathodes for LIBs in electric vehicle (EV) application and have become crucial components in the fight against global warming. However, the surging demand for LIBs has led to an extremely tight supply. The EV sector has already dominated the LIB market, even though EV sales were only 2–3% of total passenger vehicle sales in 2020. EV sales are expected to grow 10-fold by the end of this decade, and close to 90% of the total LIB demand will come from the EV sector. As a result, LIB manufacturers must aggressively ramp up cell production to keep pace with the immense growth of the EV market, a quest that brings scrutiny to the cost and sustainability of current LIB manufacturing practices. Here, cathodes are a critical component that largely determines the energy density and 40–50% of the total cell cost in LIBs. Rigorous consideration of the cathode performance and material cost is crucial in sustaining EV adoption. In this Viewpoint, we discuss why using cobalt in cathodes is unsustainable in the long run and highlight the features of cobalt-free cathodes.
25 ENERGY STORAGE↗
Low-cobalt and cobalt-free, high-energy cathode materials for lithium batteries
Described herein are low or no-cobalt materials useful as electrode active materials in a cathode for lithium or lithium-ion batteries. For example, compositions of matter are described herein, such as electrode active materials that can be incorporated into an electrode, such as a cathode. The disclosed electrode active materials exhibit high specific energy and voltage, and can also exhibit high rate capability and/or long operational lifetime.
Manthiram, Arumugam↗
Influence of Calendering on the Electrochemical Performance of LiNi 0.9 Mn 0.05 Al 0.05 O 2 Cathodes in Lithium-Ion Cells
Electrode calendering is a necessary process used in industry to improve the volumetric capacity of lithium-ion batteries. However, calendering high-nickel cathodes leads to electrode particle pulverization, raising concerns of a reduced cycle life due to parasitic side reactions. We present here an investigation of the impact of calendering on the morphology and electrochemical performance of the cobalt-free layered oxide cathode LiNi 0.9 Mn 0.05 Al 0.05 O 2 (NMA-90). We find that secondary particle pulverization and fusion simultaneously occur at sufficiently high pressures. The initial surface area of the cathode is shown to increase with the degree of calendering, despite the higher likelihood of secondary particle fusion. Long-term cycling of full coin cells assembled with the NMA-90 cathode and the graphite anode indicates that cells with higher degrees of cathode calendering exhibit lower capacity fade compared to uncalendered cathodes. Hybrid pulse-power tests demonstrate that the usable capacity range of cells with calendered cathodes far exceeds those with uncalendered cells after long-term cycling. The improved capacity retention and pulse-power performance are attributed to the enhanced mechanical properties of the electrode after calendering that prevents loss of the primary particle contact during long-term cycling. As a result, we find that calendering high-nickel NMA-90 to industrially relevant densities does not have a detrimental effect on capacity fade, marking an important step toward commercial adoption.
25 ENERGY STORAGE↗
Gaussian processes for autonomous data acquisition at large-scale synchrotron and neutron facilities
The execution and analysis of complex experiments are challenged by the vast dimensionality of the underlying parameter spaces. Although an increase in data-acquisition rates should allow broader querying of the parameter space, the complexity of experiments and the subtle dependence of the model function on input parameters remains daunting owing to the sheer number of variables. New strategies for autonomous data acquisition are being developed, with one promising direction being the use of Gaussian process regression (GPR). GPR is a quick, non-parametric and robust approximation and uncertainty quantification method that can be applied directly to autonomous data acquisition. We review GPR-driven autonomous experimentation and illustrate its functionality using real-world examples from large experimental facilities in the USA and France. We introduce the basics of a GPR-driven autonomous loop with a focus on Gaussian processes, and then shift the focus to the infrastructure that needs to be built around GPR to create a closed loop. Finally, the case studies we discuss show that Gaussian-process-based autonomous data acquisition is a widely applicable method that can facilitate the optimal use of instruments and facilities by enabling the efficient acquisition of high-value datasets.
36 MATERIALS SCIENCE↗
In–Depth Analysis of the Degradation Mechanisms of High–Nickel, Low/No–Cobalt Layered Oxide Cathodes for Lithium–Ion Batteries
A rational compositional design of high-nickel, cobalt-free layered oxide materials for high-energy and low-cost lithium-ion batteries would be expected to further propel the widespread adoption of electric vehicles (EVs), yet a composition with satisfactory electrochemical properties has yet to emerge. The previous work has demonstrated a promising LiNi 0.883 Mn 0.056 Al 0.061 O 2 (NMA-89) composition that outperformed high-nickel, cobalt-containing analogs in cycling stability and maintained a comparable rate performance and thermal stability. Herein, the capacity fading mechanism of NMA-89 in a pouch full cell with a 4.2 V cutoff is compared to that of its cobalt-containing analogs. The results reveal that particle cracking in LiNi 0.89 Mn 0.055 Co 0.055 O 2 (NMC-89) and LiNi 0.883 Co 0.053 Al 0.064 O 2 (NCA-89) leads to a loss of active material and an increase in surface area, thereby exacerbating structural and surface instabilities, accelerating impedance and polarization growth, and ultimately reducing their capacity retentions. LiNi 0.89 Mn 0.044 Co 0.042 Al 0.013 Mg 0.011 O 2 (NMCAM-89) and NMA-89 experience subdued surface reactions and maintain spherical particle structures, both of which are conducive to their capacity retentions during long-term cycling. Furthermore, this investigation offers insights into how specific transition-metal ions dictate the electrochemical stability of high-Ni layered oxide cathode materials, highlights the benefit of Mn-Al combination in NMA-89, and presents potential strategies to further enhance the performance of this novel class of cathode materials.
degradation mechanisms↗
Intrinsic Li Distribution in Layered Transition-Metal Oxides Using Low-Dose Scanning Transmission Electron Microscopy and Spectroscopy
Understanding Li distribution in layered lithium transition-metal oxide (LiTMO) cathodes in Li-ion batteries has been a major challenge at the atomic scale and nanoscale. Li is extremely difficult to study by transmission electron microscopy (TEM) because the high-energy electrons impart significant energy and cause massive migration. Here, we directly map the intrinsic spatial distribution and bonding of Li in LiNiO 2 -layered cathode materials using low-dose and low-loss electron energy loss spectroscopy (EELS). EELS spectra of the Li–K edge are measured simultaneously with O–K and Ni–L, M 3,2 edges from layered, cation-mixed, and rock-salt phases and directly matched with atomic-resolution scanning TEM images to correlate the changes in peak intensities and positions to the stoichiometry changes with continual loss of Li and O. Changes in the Li content in the LiNiO 2 particles as a function of electron beam dose are studied by sequential Li spectroscopic mapping. We show that the “intrinsic” Li distribution can be observed using a total dose of less than ~1.5 × 10 8 e – nm –2 at an accelerating voltage of 80 kV. The method of nanoscale mapping of Li distribution introduced in this study is applicable to high-Ni LiTMO cathode materials (>89% of Ni) as well as LiNiO 2 . Further study on the extra peaks of the Li–K edge reveals that the peak at ~59 eV is from the Li ions intercalated in between NiO 2 layers barely interacting with each other with less Li K shell electrons pulled to the L shell electrons in NiO 2 . Furthermore, the results shown here provide improved low-loss TEM characterization approaches that can be used to understand the intrinsic fundamental behaviors in Li-ion batteries.
25 ENERGY STORAGE↗
High–Nickel NMA: A Cobalt–Free Alternative to NMC and NCA Cathodes for Lithium–Ion Batteries
High-nickel LiNi 1–x–y Mn x Co y O 2 (NMC) and LiNi 1–x–y Co x Al y O 2 (NCA) are the cathode materials of choice for next-generation high-energy lithium-ion batteries. Both NMC and NCA contain cobalt, an expensive and scarce metal generally believed to be essential for their electrochemical performance. Herein, a high-Ni LiNi 1–x–y Mn x Al y O 2 (NMA) cathode of desirable electrochemical properties is demonstrated benchmarked against NMC, NCA, and Al–Mg-codoped NMC (NMCAM) of identical Ni content (89 mol%) synthesized in-house. Despite a slightly lower specific capacity, high-Ni NMA operates at a higher voltage by ≈40 mV and shows no compromise in rate capability relative to NMC and NCA. In pouch cells paired with graphite, high-Ni NMA outperforms both NMC and NCA and only slightly trails NMCAM and a commercial cathode after 1000 deep cycles. Further, the superior thermal stability of NMA to NMC, NCA, and NMCAM is shown using differential scanning calorimetry. Here, considering the flexibility in compositional tuning and immediate synthesis scalability of high-Ni NMA very similar to NCA and NMC, this study opens a new space for cathode material development for next-generation high-energy, cobalt-free Li-ion batteries.
25 ENERGY STORAGE↗
Energy Sciences Network (ESnet): Nuclear Physics Network Requirements Review Report
In May 2019, ESnet and the Office of Nuclear Physics (NP) of the DOE Office of Science organized an ESnet requirements review of NP-supported activities. Preparation for this event included identification of key stakeholders to the process: program and facility management, research groups, technology providers, and a number of external observers. These individuals were asked to prepare formal case study documents about their relationship to the NP program to build a complete understanding of the current, near-term, and long-term status, expectations, and processes that will support the science going forward. A series of pre-planning meetings better prepared case study authors for this task and facilitated a smooth transition to the in-person review.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Workshop Report on Basic Research Needs for Scientific Machine Learning: Core Technologies for Artificial Intelligence
Scientific Machine Learning (SciML) and Artificial Intelligence (AI) will have broad use and transformative effects across the Department of Energy. Accordingly, the January 2018 Basic Research Needs workshop identified six Priority Research Directions (PRDs). The first three PRDs describe foundational research themes that correspond to the need for domain-awareness (PRD #1), interpretability (PRD #2), and robustness (PRD #3). The other three PRDs describe capability research themes and correspond to the three major use cases for massive scientific data analysis (PRD #4), machine learning-enhanced modeling and simulation (PRD #5), and intelligent automation and decision-support for complex systems (PRD #6). The Priority Research Directions provide a sound basis for a coherent, long-term research and development strategy in SciML and AI. Over the last decade, DOE investments in applied mathematics have laid the groundwork for the type of basic research that will underpin key advances in the six PRDs. Such advances will build on the work from leading researchers in optimization, linear algebra, high-performance solvers and algorithms, multiscale modeling and simulation, complex systems research, uncertainty quantification, and the new basic research areas that will emerge from the pursuit of transformative technologies.
97 MATHEMATICS AND COMPUTING↗
Martian aeolian processes, sediments, and features
In this review of the aeolian regime on Mars, consideration is given to the sources and characteristics of the particles that are involved in aeolian processes and the winds that are required to set grains into motion. Dust storms are reviewed and previous observations and the mechanisms of dust-storm generation are assessed. Various aeolian features, including dunes and albedo features, as well as windblown mantle deposits are discussed. In planning for future missions to Mars, aeolian processes must be taken into account. Surface modifications by the wind and windblown deposits can influence remote-sensing observations, affect sampling strategies, and have detrimental effects on manned and unmanned spacecraft on the surface.
Greeley, Ronald↗
MECA Workshop on Dust on Mars 3
Articles and abstracts of articles presented at this workshop are given. It was the goal of the workshop to stimulate cooperative research on, and discussion of, dust related processes on Mars, and to provide background information and help in planning of the Mars Observer mission. These topics are considered: How is dust ejected from the Martian surface into the atmosphere; How does the global atmospheric circulation affect the redistribution of dust on Mars; Are there sources and sinks of dust on Mars, if so, where are they and how do they vary in time; and How many components of dust are there on Mars, and what are their properties. There were four primary discussion sessions: (1) Dust in the atmosphere; (2) Dust on the surface; (3) Dust properties; and (4) Dust observations from future spacecraft missions.
Lee, Steven↗
Martian Clouds Data Workshop
The major topics covered were a discussion of the structure of relational data base systems and features of the Britton Lee Relational Data Base Management System (RDBMS); a discussion of the workshop's objectives, approach, and research scenarios; and an overview of the Atmospheres Node User's Guide, which details the datasets stored on the Britton Lee, the structure of the query and data analysis system, and examples of the exact menu screens encountered. Also discussed were experience with the system, review of the system performance, and a strategy to produce queries and performance data retrievals of mutual interest. The goals were defined as examining correlations between cloud occurrence, water vapor abundance, and surface properties.
Lee, Steven↗