A Co- and Ni-Free P2/O3 Biphasic Lithium Stabilized Layered Oxide for Sodium-Ion Batteries and its Cycling Behavior
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99 GENERAL AND MISCELLANEOUS↗
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Interphase Stabilization of LiNi 0.5 Mn 1.5 O 4 Cathode for 5 V–Class All–Solid–State Batteries
Employing high voltage cobalt-free spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) as a cathode is promising for high energy density and cost-effectiveness, but it has challenges in all-solid-state batteries (ASSBs). Here, it is revealed that the limitation of lithium argyrodite sulfide solid electrolyte (Li 6 PS 5 Cl) with the LNMO cathode is due to the intrinsic chemical incompatibility and poor oxidative stability. Through a careful analysis of the interphase of LNMO, it is elucidated that even the halide solid electrolyte (Li 3 InCl 6 ) with high oxidative stability can be decomposed to form resistive interphase layers with LNMO in ASSBs. Interestingly, with Fe-doping and a Li 3 PO 4 protective layer coating, LNMO with Li 3 InCl 6 displays stable cycle performance with a stabilized interphase at a high voltage (≈4.7 V) in ASSBs. The enhanced interfacial stability with the extended electrochemical stability window through doping and coating enables high electrochemical stability with LNMO in ASSBs. Furthermore, this work provides guidance for employing high-voltage cathodes in ASSBs and highlights the importance of stable interphases to enable stable cycling in ASSBs.
25 ENERGY STORAGE↗
Compositionally gradient nickel-rich cathode materials and methods for the manufacture thereof
The present invention relates to lithium rechargeable battery cathode materials. More specifically, the cathode materials are compositionally gradient nickel-rich cathode materials produced using single-source composite precursor materials containing inorganic and/or metalorganic salts of lithium, nickel, manganese, and cobalt. Methods and systems for manufacturing the cathode materials by a combined spray pyrolysis/fluidized bed process are also disclosed.
Kodenkandath, Thomas A.↗
Thermal dynamics of P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode materials for sodium ion batteries studied by in situ analysis
Cobalt-free layered Na 0.67 Ni 0.33 Mn 0.67 O 2 is an attractive cathode material for sodium ion batteries. The thermal stability of cathode materials is crucial to their practical applications. In the current work, we investigate structural and morphological evolution in P2-type Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode materials during annealing via in situ synchrotron X-ray diffraction and transmission electron microscopy. Insights are obtained from the two complementary in situ characterizations (at different length scales) in term of the thermal stability of P2-Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode materials. Here, the results indicate that the hexagonal P2 phase remains unchanged during the heat treatment process, and thermally driven expansion/contraction of lattice parameters exhibit an anisotropic character in the a and c directions. In addition, interfaces/grain boundaries play an important role in the structural stability, which leads to the distinct morphological evolution between the polycrystalline and single-crystal particles.
25 ENERGY STORAGE↗
In Situ ATR-FTIR Study of the Cathode–Electrolyte Interphase: Electrolyte Solution Structure, Transition Metal Redox, and Surface Layer Evolution
We present a study of the lithium nickel manganese cobalt oxide (LiNi 0.6 Mn 0.2 Co 0.2 O 2 , NMC622) cathode-electrolyte interphase (CEI) during galvanostatic charging and discharging using in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) methods to investigate the voltage dependent electrolyte solution structure changes at the interface, transition metal (TM) redox chemistry, and cathode/electrolyte interfacial layer evolution. Furthermore, our in situ cell design provides both reliable electrochemical device testing and strong FTIR vibrational absorption signals near the cathode surface. Specifically, advanced spectral analysis elucidates changes of near-surface Li+ ion (de)solvation by solvent molecules during galvanostatic cycling. Moreover, cathode metal-oxygen vibrational absorptions, sensitive to TM redox behaviors and subsequent local structural variations, were correlated to cathode de-lithiation (and lithiation) and electrolyte solution structure changes. In addition, we have detected the formation and evolution of a CEI surface layer on the NMC622 cathode that contributes to the cell's capacity fade.
25 ENERGY STORAGE↗
Enabling high areal capacity for Co-free high voltage spinel materials in next-generation Li-ion batteries
The rapidly growing technological demand for lithium-ion batteries has prompted the development of novel cathode materials with high energy density, low cost, and improved safety. High voltage spinel, LiNi 0.5 Mn 1.5 O 4 (LNMO), is one of the most promising candidates yet to be commercialized. The two primary obstacles for this material are the inferior electronic conductivity and fast capacity degradation in full cells due to the high operating voltage. By systematically addressing these limitations, we successfully develop a thick LNMO electrode with areal capacity loadings up to 3 mAh·cm –2 . The optimized thick electrode is paired with a commercial graphite anode at both the coin cell and pouch cell level, achieving a full cell capacity retention as high as 72% and 78%, respectively, after 300 cycles. We attribute this superior cycling stability to careful optimizations of cell components and testing conditions, with a specific focus improving electronic conductivity and high voltage compatibility. These results suggest precise control of materials quality, electrode architecture and electrolyte optimization can soon support the development of a cobalt-free battery system based on a thick LNMO cathode (>4 mAh·cm 2 ), which will eventually meet the needs of next-generation Li-ion batteries with reduced cost, improved safety, and assured sustainability.
25 ENERGY STORAGE↗
Single Cobalt Sites Dispersed in Hierarchically Porous Nanofiber Networks for Durable and High-Power PGM-Free Cathodes in Fuel Cells
Increasing catalytic activity and durability of atomically dispersed metal–nitrogen–carbon (M–N–C) catalysts for the oxygen reduction reaction (ORR) cathode in proton-exchange-membrane fuel cells remains a grand challenge. In this study, a high-power and durable Co–N–C nanofiber catalyst synthesized through electrospinning cobalt-doped zeolitic imidazolate frameworks into selected polyacrylonitrile and poly(vinylpyrrolidone) polymers is reported. The distinct porous fibrous morphology and hierarchical structures play a vital role in boosting electrode performance by exposing more accessible active sites, providing facile electron conductivity, and facilitating the mass transport of reactant. The enhanced intrinsic activity is attributed to the extra graphitic N dopants surrounding the CoN 4 moieties. The highly graphitized carbon matrix in the catalyst is beneficial for enhancing the carbon corrosion resistance, thereby promoting catalyst stability. The unique nanoscale X-ray computed tomography verifies the well-distributed ionomer coverage throughout the fibrous carbon network in the catalyst. The membrane electrode assembly achieves a power density of 0.40 W cm –2 in a practical H 2 /air cell (1.0 bar) and demonstrates significantly enhanced durability under accelerated stability tests. The combination of the intrinsic activity and stability of single Co sites, along with unique catalyst architecture, provide new insight into designing efficient PGM-free electrodes with improved performance and durability.
25 ENERGY STORAGE↗
Processes for Environmentally Friendly and Low-Cost Recycling of Lithium-Ion Batteries (CRADA Final Report)
NLR will help ACE Green Recycling evaluate and develop its processes for environmentally friendly and low-cost recycling of graphite, lithium-iron phosphate (LFP), and other cathode materials from spent lithium-ion batteries.
25 ENERGY STORAGE↗
Progress of Nanotechnology for Lithium-Sulfur Batteries
Lithium-Sulfur (Li-S) battery has been proposed and investigated since the 1960s as an effective energy storage device via reversible electrochemical reactions. As the fast development and commercialization of Li-ion battery (LIB) technology kept moving forward, no breakthroughs have been attained to solve critical technical issues facing Li-S batteries during the following decades. In the year 2000s, Li-S batteries reattracted significant interests in the research field owing to their low-cost advantages, high theoretical specific energy of 2600 Wh kg -1 , which is at least 3 times higher than the current LIB technology. The low-cost and high abundance of sulfur (i.e., the cathode active material), make Li-S batteries more appealing than LIBs given the fact that the latter use critical materials such as cobalt and nickel in the manufacturing of the cathodes. Moreover, the high-energy and low-cost features make the Li-S battery a promising energy storage technology in practical applications such as portable devices, electric vehicles, and grid storage when coupled with the harvesting of solar or wind renewable energies. For example, since 2007, SION Power Corporation (Tucson, USA) and Oxis Energy (UK) made progress towards the commercialization of Li-S batteries with products showing specific energies over 350 Wh kg -1 for powering electric vehicles. To be on a par with the current LIB technology, the ultimate goal of achieving 500 Wh kg -1 for Li-S battery will make it more competitive for widespread commercialization.
Li, Mengya↗
Interfacial Chemistry Involved in Selective Separation of NMC/LMO and LCO/LMO Binary Cathode Materials by Froth Flotation Using Oleic Acid
The variability in cathode compositions within recycled lithium-ion battery (LIB) feedstocks poses a significant challenge to efficient downstream refining processes. This study demonstrates the feasibility of using froth flotation with oleic acid as a collector to selectively separate lithium nickel-manganese-cobalt oxide (NMC) and lithium cobalt oxide (LCO) from lithium manganese oxide (LMO) materials. Laboratory-scale flotation tests achieved an 80% separation efficiency in a single stage, producing a froth product with >90% purity of NMC/LCO at approximately 90% yield. Concurrently, the LMO materials were enriched in the sink product with ∼90% purity and ∼90% yield. This approach was further validated using recycled cathode materials, confirming its applicability to realistic feedstocks. The underlying mechanism governing the selective separation of NMC/LCO from LMO was investigated using ζ-potential measurements, contact angle measurements, bubble-particle attachment experiments, and X-ray photoelectron spectroscopy (XPS) analysis. Both contact angle and bubble-particle attachment results confirmed that oleic acid adsorption rendered NMC and LCO surfaces hydrophobic, thereby enhancing flotation recovery. At pH 5, oleic acid adsorbed preferentially onto NMC and LCO surfaces via electrostatic interactions, while exhibiting minimal adsorption on LMO surfaces. However, separation efficiency deteriorated at higher pH, which was attributed to the co-flotation of LMO materials caused by oleate chemisorption on MnOH + species. This work establishes froth flotation as a viable cathode/cathode separation strategy, providing a low-cost, scalable pathway to preconcentrate and enrich nickel-rich and cobalt-rich cathode active materials from incompatible cathode chemistries for direct recycling or hydrometallurgical processing. Furthermore, this study reveals, for the first time, the mechanism of oleate adsorption on the surface of different cathode materials.
PH↗
Atomic-Scale Observation of O1 Faulted Phase-Induced Deactivation of LiNiO 2 at High Voltage
LiNiO 2 and cobalt-free ultrahigh-Ni content cathodes suffer from rapid capacity loss and severe chemomechanical degradation, especially when operated at high voltages. Here, by cycling LiNiO 2 up to 4.7 V, we report the atomic-scale observation of O1 faulted phase-induced deactivation of LiNiO 2 . We found that although a thin layer of O3 phase forms on the particle surface by reversible O3 → O1 transformation during discharge, the bulk interior still maintains the O1 faulted phase, leading to rapid capacity loss of LiNiO 2 . Moreover, the atomic configuration of the O1/O3 interface is investigated comprehensively. We found that the misfit along the c axes of the O1 and O3 phases results in the formation of misfit dislocations, whereby cation mixing is promoted at dislocation cores. Further, a transition zone with continuous shear along the a-b plane is uncovered between the O1 and O3 phases for the first time. Besides, severe oxygen loss-induced pore formation and concurrent rock salt transformation are also identified.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Advanced Slug-flow Manufacturing of Uniform and Tunable Battery Cathode Particles
Advanced Slug-flow Manufacturing of Uniform and Tunable Battery Cathode Particles
25 ENERGY STORAGE↗
Direct Recycling R&D at the ReCell Center
The expected rapid growth in electric vehicle deployment will inevitably be followed by a corresponding rise in the supply of end-of-life vehicles and their lithium-ion batteries (LIBs). The batteries may be reused, but will eventually be spent and provide a potential domestic resource that can help supply materials for future battery production. However, commercial recycling processes depend on profits from recovery of cobalt, use of which is being reduced in new cathode chemistries. The U.S. Department of Energy, therefore, established the ReCell Center in early 2019 to develop robust LIB recycling technology that would be economical even for batteries that contain no cobalt. The central feature of the technology is recovery of the cathode material with its unique crystalline cathode morphology intact in order to retain its value and functionality. Other materials are recovered as well in order to maximize revenues and minimize waste-handling costs. Analysis and modeling serve to evaluate and compare process options so that we can identify those that will be most economical while still minimizing energy use and environmental impacts. This paper provides background and describes highlights of the center’s first 2 years of operation.
Gaines, Linda (ORCID:0000000237263387)↗
Dual conductor surface modified SOFC cathode particles and methods of making same
A novel method to produce ALD films disposed on powders is disclosed. Examples include the formation of a cobalt doped zirconia (CDZ), hafnia, and cobalt doped hafnia (CDH) films on lanthanum strontium cobalt iron oxide (LSCF) powder for solid oxide fuel cell cathodes. The coated powders are sintered into porous cathodes that have utility for preventing the migration of cations in the powder to the surface of the sintered cathode and/or other performance enhancing attributes.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Co-Free Cathode Materials and Their Novel Architectures
To enable cobalt-free LiNi 0.5 Mn 1.5 O 4 (LNMO) electrode and novel electrolyte formulation for use in next-generation Li-ion batteries (LIB) capable of high energy density, long cycle life and low cost, several methods were developed throughout this project. To enhance the performance of LNMO, Fe-doping on LNMO, laser treatment and atomic layer deposition (ALD) were adopted. Moreover, dry electrode method has successfully helped to fabricate ultra-high loading LNMO with stable performance. The improvement at anode side includes ALD-coating as well as pre-lithiation of graphite anode. In the novel electrolyte development, it was found that all-fluorinated electrolyte with appropriate additives can effectively extend both cycle and calendar life of LNMO full cells at practical loadings. Additional diagnosis of LNMO full cells showed that different types of carbon and porosity of separator play a critical role in the success of LNMO’s high voltage operation. The combined effort throughout the project pushed forward the understanding and commercialization of LNMO at practical level.
25 ENERGY STORAGE↗
The Riddle of Dark LLZO: Cobalt Diffusion in Garnet Separators of Solid‐State Lithium Batteries
Abstract Solid‐state batteries (SSBs) with a Li 7 La 3 Zr 2 O 12 (LLZO) garnet electrolyte are attracting much attention as robust and safe alternative to conventional lithium‐ion batteries. Technical challenges in the practical implementation of garnet SSBs are related to the need for high‐temperature sintering, which often leads to undesirable chemical reactions with the cathode material. While these reactions are well understood for composite cathodes, very little is known about similar processes between cathode and separator during battery fabrication. This work focuses on understanding the processes between the composite LiCoO 2 ‐LLZO cathode and the LLZO separator and how they affect the battery performance. The extensive diffusion of Co‐ions within LLZO, which leads to the often‐observed LLZO darkening, is shown to have a significant impact on ionic conductivity, electronic conductivity, and dendrite stability of the separator. Experimental data coupled with large‐scale molecular dynamics simulations uncover the diffusion mechanism for Co‐ions and identify secondary phases that form during these interactions. In addition to extensive Co‐ion diffusion within the grains, a non‐uniform segregation of Co‐ions at grain boundaries is found leading to the formation of three distinct Co‐containing phases. This work offers a general approach to studying the fundamental ion diffusion processes that occur during the fabrication of oxide SSBs.
electrochemical properties↗
Depth-dependent valence stratification driven by oxygen redox in lithium-rich layered oxide
Abstract Lithium-rich nickel-manganese-cobalt (LirNMC) layered material is a promising cathode for lithium-ion batteries thanks to its large energy density enabled by coexisting cation and anion redox activities. It however suffers from a voltage decay upon cycling, urging for an in-depth understanding of the particle-level structure and chemical complexity. In this work, we investigate the Li 1.2 Ni 0.13 Mn 0.54 Co 0.13 O 2 particles morphologically, compositionally, and chemically in three-dimensions. While the composition is generally uniform throughout the particle, the charging induces a strong depth dependency in transition metal valence. Such a valence stratification phenomenon is attributed to the nature of oxygen redox which is very likely mostly associated with Mn. The depth-dependent chemistry could be modulated by the particles’ core-multi-shell morphology, suggesting a structural-chemical interplay. These findings highlight the possibility of introducing a chemical gradient to address the oxygen-loss-induced voltage fade in LirNMC layered materials.
25 ENERGY STORAGE↗
Recovery of critical elements from end-of-life lithium ion batteries with supported membrane solvent extraction
Single-stage and multi-stage systems and methods for the recovery of critical elements in substantially pure form from lithium ion batteries are provided. The systems and methods include supported membrane solvent extraction using an immobilized organic phase within the pores of permeable hollow fibers. The permeable hollow fibers are contacted by a feed solution on one side, and a strip solution on another side, to provide the simultaneous extraction and stripping of elements from dissolved lithium ion cathode materials, while rejecting other elements from the feed solution. The single- and multi-stage systems and methods can selectively recover cobalt, manganese, nickel, lithium, aluminum and other elements from spent battery cathodes and are not limited by equilibrium constraints as compared to traditional solvent extraction processes.
Bhave, Ramesh R.↗