Primary Particles Research Articles

Carbonated Beverage Chemistry for High-Voltage Battery Cathodes.

Advanced lithium-ion batteries utilize high upper cut-off voltages up to 4.8V versus lithium metal to reach extraordinary energy densities. Such a harsh environment challenges the cathode stability and requires the construction of robust cathode electrolyte interphases at their electrochemical interface. Inspired by carbonated beverages with supersaturated CO2, here we propose a surface modification strategy that produces effective passivation layer of low modulus from the weakest link. CO2 bubbles preferentially nucleate and grow at rough surfaces, which in oxide cathodes are also the local regions offering fast degradation pathway. Metal ion exchange on carbonated layer assist the construction of highly elastic interface under the guidance of packing factor. Our method enables surface reconstruction at both primary and secondary particle levels, for various cathodes exemplified by high-voltage LiNi0.8Co0.1Mn0.1O2 and LiCoO2. Remarkably, with ultra-high upper cut-off voltage of 4.8V versus Li+/Li, over 235 mAh g-1 discharge capacity and over 900W h kg-1 discharge energy at cathode level, ∼90% capacity retention can be obtained for LiNi0.8Co0.1Mn0.1O2 over 100 cycles at 0.5 C with commercial carbonate electrolytes. This carbonated beverage chemistry is promising for constructing high-quality surface passivation in many extreme-condition applications beyond battery cathodes. This article is protected by copyright. All rights reserved.

Scanning Electrochemical Microscopy Meets Optical Microscopy: Probing the Local Paths of Charge Transfer Operando in Booster-Microparticles for Flow Batteries.

Understanding the oxidation/reduction dynamics of secondary microparticles formed from agglomerated nanoscale primary particles is crucial for advancing electrochemical energy storage technologies. In this study, the behavior of individual copper hexacyanoferrate (CuHCF) microparticles is explored at both global and local scales combining scanning electrochemical microscopy (SECM), for electrochemical interrogation of a single, but global-scale microparticle, and optical microscopy monitoring to obtain a higher resolution dynamic image of the local electrochemistry within the same particle. Chronoamperometric experiments unveil a multistep oxidation/reduction process with varying dynamics. On the one hand, the global SECM analysis enables quantifying the charge transfer as well as its dynamics at the single microparticle level during the oxidation/reduction cycles by a redox mediator in solution. These conditions allow mimicking the charge storage processes in these particles when they are used as solid boosters in redox flow batteries. On the other hand, optical imaging with sub-particle resolution allows the mapping of local conversion rates and state-of-charge within individual CuHCF particles. These maps reveal that regions of different material loadings exhibit varying charge storage capacities and conversion rates. The findings highlight the significance of porous nanostructures and provide valuable insights for designing more efficient energy storage materials.

Contribution of fluorescent primary biological aerosol particles to low-level Arctic cloud residuals

Abstract. Mixed-phase clouds (MPCs) are key players in the Arctic climate system due to their role in modulating solar and terrestrial radiation. Such radiative interactions rely, among other factors, on the ice content of MPCs, which is regulated by the availability of ice-nucleating particles (INPs). While it appears that INPs are associated with the presence of primary biological aerosol particles (PBAPs) in the Arctic, the nuances of the processes and patterns of INPs and their association with clouds and moisture sources have not been resolved. Here, we investigated for a full year the abundance of and variability in fluorescent PBAPs (fPBAPs) within cloud residuals, directly sampled by a multiparameter bioaerosol spectrometer coupled to a ground-based counterflow virtual impactor inlet at the Zeppelin Observatory (475 m a.s.l.) in Ny-Ålesund, Svalbard. fPBAP concentrations (10−3–10−2 L−1) and contributions to coarse-mode cloud residuals (0.1 to 1 in every 103 particles) were found to be close to those expected for high-temperature INPs. Transmission electron microscopy confirmed the presence of PBAPs, most likely bacteria, within one cloud residual sample. Seasonally, our results reveal an elevated presence of fPBAPs within cloud residuals in summer. Parallel water vapor isotope measurements point towards a link between summer clouds and regionally sourced air masses. Low-level MPCs were predominantly observed at the beginning and end of summer, and one explanation for their presence is the existence of high-temperature INPs. In this study, we present direct observational evidence that fPBAPs may play an important role in determining the phase of low-level Arctic clouds. These findings have potential implications for the future description of sources of ice nuclei given ongoing changes in the hydrological and biogeochemical cycles that will influence the PBAP flux in and towards the Arctic.

Single-Crystal P2-Na0.67Mn0.67Ni0.33O2 Cathode Material with Improved Cycling Stability for Sodium-Ion Batteries.

Layered oxides constitute one of the most promising cathode materials classes for large-scale sodium-ion batteries because of their high specific capacity, scalable synthesis, and low cost. However, their practical use is limited by their low energy density, physicochemical instability, and poor cycling stability. Aiming to mitigate these shortcomings, in this work, we synthesized polycrystalline (PC) and single-crystal (SC) P2-type Na0.67-δMn0.67Ni0.33O2 (NMNO) cathode materials through a solid-state route and evaluated their physicochemical and electrochemical performance. The SC-NMNO cathode with a large mean primary particle size (D50) of 12.7 μm was found to exhibit high cycling stability leading to 47% higher capacity retention than PC-NMNO after 175 cycles at 1C rate in the potential window 4.2-1.5 V. This could be attributed to the effective mitigation of parasitic side reactions at the electrode-electrolyte interface and suppressed intergranular cracking induced by anisotropic volume changes. This is confirmed by the lower volume variation of SC-NMNO (ΔV ∼ 1.0%) compared to PC-NMNO (ΔV ∼ 1.4%) upon charging to 4.2 V. Additionally, the SC-NMNO cathode displayed slightly higher thermal stability compared to PC-NMNO. Both cathodes exhibited good chemical stability against air and water exposure, thus enabling material storage/handling in the ambient atmosphere as well as making them suitable for aqueous processing. In this regard, PC-NMNO was investigated with two low-cost aqueous binders, carboxymethyl cellulose, and sodium trimetaphosphate, which exhibited higher binding strength and displayed excellent electrochemical performance compared to PVDF, which could potentially lead to significant cost reduction in electrode manufacturing.

Oxidation-induced variations in the physical and fragmentation characteristics of exhaust soot from DMC-diesel blend: Effect of NO presence in the air atmosphere

This study investigated the changes in physical properties (including morphology, primary particle diameter, fractal dimension, and nanostructure) and fragmentation characteristics of exhaust soot from a modern direct injection diesel engine fueled with diesel (D100) and its blend with 7 vol% of dimethyl carbonate (DMC7) during oxidation processes in air and air-NO atmospheres. Soot particles (D100 soot and DMC7 soot) with specific oxidation degrees (0%, 20%, 50%, and 80%) were produced using a thermogravimetric analyzer, then applied to a high-resolution transmission electron microscopy to generate images. The results exhibited that the morphology for D100 soot and DMC7 soot transformed similarly through oxidation, experiencing an increase in fractal dimension, and a decrease in primary particle diameter, while the introduction of NO to the air accelerated these transformations. Additionally, the nanostructure of both soot particles was gradually ordered through oxidation, as evidenced by longer fringe length, narrower separation distance, and lower tortuosity, while DMC7 soot showed lower order degree compared to D100 soot. Interestingly, the ordering processes of soot nanostructure were decelerated as NO was involved in the oxidation process. Furthermore, the aggregate fragmentation rate for both soot particles declined over the oxidation process, while the possibility for primary particle fragmentation increased overall. Moreover, DMC7 soot exhibited significantly lower aggregate fragmentation rate and higher possibility for primary particle fragmentation than D100 soot at the same oxidation stage. This suggests that DMC7 soot is more susceptible to internal oxidation compared to D100 soot. Furthermore, the presence of NO in the air promoted aggregate fragmentation, while reducing the possibility of primary particle fragmentation.

SPAN secondary particles enabled high energy density Lithium-Sulfur battery

High-areal-capacity electrodes and lean electrolyte are practical approaches for batteries to enhance their energy density, while it’s challenge for the lithium-sulfur batteries using nano-sized sulfurized polyacrylonitrile (SPAN) cathodes due to the sluggish charge transportation. Here, a spray-drying (SD) technique for mass production of micron-sized SPAN secondary particles (PC-SPAN) with composite coating is proposed. The composite involves polydopamine (PDA), polyacrylic acid (PAA) and polyvinyl alcohol (PVA) that physiochemically crosslinking. The rich catecholamine, hydroxyl and carboxyl groups not only construct strong and flexible adhesion among the SPAN primary particles to keep the electrode integrity, but also render built-in ion passage within the secondary particles to allow the electrode working under lean electrolyte condition. Consequently, PC-SPAN electrode with a high areal loading of 8.4 mg cm−2 delivers a higher specific capacity of 547.4 mAh g−1 at 0.3C when that of SPAN is less than 400.0 mAh g−1. In the meantime, prototype Li-SPAN battery with high energy density of 530.2 Wh kg−1 is achieved using PC-SPAN electrode with an areal capacity of 19.1 mAh cm−2 and low electrolyte/SPAN ratio of 0.93 μL mg−1, which demonstrates the feasibility of this strategy toward applicable high energy LSBs.

Capture enhanced neutron irradiation for the treatment of the Alzheimer Disease: Micro-nanodosimetric characterization of beta amyloid peptide samples

Alzheimer Disease (AD) is the most common cause of dementia. 46.8 million people live with AD worldwide, with numbers projected to almost double every 20 years. The etiological mechanisms underlying the neuropathological changes in AD remain unclear. The beta amyloid peptide Aβ is considered to be the main culprit of the pathological processes. NECTAR (NEutron Capture-enhanced Treatment of neurotoxic Amyloid aggRegates) project proposes an alternative and revolutionary strategy to address AD, investigating the safety, feasibility and effectiveness of a Capture-Enhanced Neutron Irradiation to structurally damage Aβ aggregates, by exploiting capture agent vectors containing B-10 and Gd-157.Among many others, one of the goals of the project is to perform calculations and measurements of microdosimetric and nanodosimetric quantities to characterize the effect of reaction products at local level and to link it to the fibrils depolymerization process. In this framework, a new low-pressure tissue-equivalent proportional counter (TEPC) was designed and developed. The system is a wall-free TEPC able to measure micro-nanometric dose deposition for different biological samples. It is characterized by two main features: i) a wall-less structure allows the charged particles produced by the sample to access the sensitive volume, where their effects are studied; ii) a trigger system enables the assessment of the number of ionizations induced in the sensitive volume related to a single primary particle for obtaining nandosimetric information.The prototype system was tested in the PGNAA (Prompt Gamma Neutron Activation Analysis) facility of the LENA reactor (Pavia) to directly study secondary particles from Aβ fibrils, loaded with Boron. Results of the micro-nanodosimetric characterization of high LET secondaries from Aβ-fibrils were compared to a reference Boron sample. For a 500 nm simulated site size, the presence of Boron in the Aβ sample greatly populates microdosimetric spectra at high lineal energy values. Instead, lower LET particles (photons, protons) from reactions on the other Aβ aggregate solution molecules populate the low lineal energy portion of the distribution.The nanodosimetric distributions highlights the presence of different field components on the nanodosimetric spectra: low LET particles (protons/electrons) produce small ionization clusters, while alpha and Lithium ions induce larger clusters, thus have a higher biological effect. The nanodosimetric measurements have been compared with Monte Carlo simulations performed with a track-structure code, showing a good agreement.This multi-level approach provides a deeper physical understanding of the mixed secondaries field coming from B-enriched target, as well as a reference for the biological effect on Aβ fibrils at nanometer level. These preliminary measurements represent the first microdosimetric and nanodosimetric characterization of the secondary mixed field directly emitted by a biological sample irradiated with neutrons.

Precision engineering of high-performance Ni-rich layered cathodes with radially aligned microstructure through architectural regulation of precursors

Microstructure engineering serves as a potent approach to counteract the mechanical deterioration of Ni-rich layered cathodes, stemming from anisotropic strain during Li+ (de)intercalation. However, a pressing challenge persists in devising a direct method for fabricating radially aligned cathodes utilizing oriented hydroxide precursors. In this study, we synthesized LiNi0.92Co0.04Mn0.04O2 oxides boasting superior radially aligned, size-refined primary particles through a combination of strategic precipitation regulation and lithiation tuning. Elongated primary particles, achieved by stepwise control of ammonia concentration and pH during particle growth, facilitate the formation of radially aligned hydroxide precursor particles. Leveraging the size-refined and radially aligned primary particles, our prepared LiNi0.92Co0.04Mn0.04O2 cathode exhibits a high discharge capacity of 229 mAh g−1 at 0.05 C, alongside excellent cycle stability, retaining 93.3% capacity after 200 cycles at 0.5 C (30 °C) in a half cell, and 86.4% capacity after 1000 cycles at 1 C (30 °C) in a full cell. Revisiting the regulation from precursor to oxide underscores the significance of controlling primary particles to maximize size perpendicular to [001] and attain suitable size along [001] during precursor precipitation and high-temperature calcination, offering valuable insights for synthesizing high-performance Ni-rich cathodes.

Multiscale structure analysis of a pH-responsive gelatin/hydroxypropyl methylcellulose phthalate blend using small-angle scattering

HypothesisHydroxypropyl methylcellulose phthalate (HPMCP) is an enteric polymer that has been employed in drug delivery systems to delay the release of the encapsulated active pharmaceutical ingredients through its pH-responsive solubility change. This has been recently demonstrated as an effective means for delaying the drug release from gelatin/HPMCP hydrogels at gastric pH values. However, structural characteristics of HPMCP agglomeration in gelatin/HPMCP hydrogels is not well understood thus limiting further tailoring of their material properties. ExperimentsWe investigated the multiscale structure of a gelatin/HPMCP hydrogel (1:1 by weight) at 37 °C, above the upper critical solution transition temperature of gelatin, between pH 2 and 6 using small-angle X-ray scattering and contrast-variation small-angle neutron scattering to understand the pH-responsive structure of HPMCP and the cross-correlation between gelatin and HPMCP. FindingsAgglomeration of HPMCP between pH 2 and 4 was evidenced by the formation of mass fractal structures, with a fractal dimension of ca. 1.7, comprising primary particles with a radius of gyration of ca. 90 Å. Blending with gelatin influenced the fractal structure of HPMCP and primary particle size. Gelatin and HPMCP exhibited negative cross-correlation in all probed length scales and pH values, which was attributed to volume-exclusion interaction in a double-network-like solution architecture.

A novel synthesis method of magnetic Janus particles for wastewater applications

HypothesisMagnetic particles are widely used in many adsorption and removal processes. Among the many types of magnetic colloids, magnetic Janus particles offer significant possibilities for the effective removal of several components from aqueous solutions. Nevertheless, the synthesis of structures integrating different types of materials requires scalable fabrication processes to overcome the limitations of the available methodologies. Herein, we hypothesized a fabrication process for dual-surface functionalized magnetic Janus particles. ExperimentsThe primary silica particles with surface-attached amine groups are further asymmetrically modified by iron oxide nanoparticles, exploiting Pickering emulsion and electroless deposition techniques. The dual surface functionality of the particles is designed for its versatility and demonstrated in two wastewater-related applications. FindingsWe show that our design can simultaneously remove chromium (VI) and phenol from aqueous solution. The fabricated magnetic-responsive Janus particles are also an effective adsorbent for genomic Deoxyribonucleic acid (DNA) and show superior performance to commercial magnetic beads. Thus, this study provides a novel platform for designing magnetic Janus particles with multifunctional surfaces for wastewater treatment applications.

Characterization of metal-bearing nanoparticles observed in loess-covered terrain: Implications for prospecting

The recent depletion of mineral resources near the Earth's surface has led to a shift in mineral exploration toward concealed deposits in covered terrain. Consequently, significant attention has been directed toward metal-bearing nanoparticles in the soil above such deposits to gain insights into the composition of concealed ore bodies.In this study, the characteristics (type, size, shape, chemical composition, and aggregation) of metal-bearing nanoparticles in ore samples of the Zhonghedi Ag-Pb-Zn polymetallic deposit and their overlying loess were systematically analyzed using transmission electron microscopy. Numerous nanoparticles containing Ag, Au, Cu, Pb, Zn, Fe, Mo, and other metallic elements were observed in the loess overlying the deposits as well as the ore samples. These nanoparticles exhibit a well-defined crystal shape, suggesting their primary particle nature. Moreover, the nanoparticles in the loess and ore samples share similarities in element distribution, size, and type, demonstrating their homologous nature. However, ore-related metal-bearing nanoparticles were not detected in samples collected from the background areas. Most metal-bearing nanoparticles in loess, excluding native particles, were oxides and sulfates, which may be attributed to oxidation of the native metal particles near the surface where oxygen fugacity increases. The elemental mapping of the nanoparticles showed that the ore-forming elements had the same distribution patterns and element assemblages to the ore material. These results indicate that metal-bearing nanoparticles in the loess have likely relationships with concealed ore bodies. Accordingly, the metal-bearing nanoparticles in the loess can provide information about concealed ore deposits, explain surface geochemical anomalies, and improve prospecting accuracy as a vector to mineralization.Routinely finding nanoparticles in transported cover remains a challenge. However, this study shows it is viable and marks substantial progress in our knowledge and comprehension of metal-bearing nanoparticles in loess-covered terrain. Evidence of their presence and association with concealed ore bodies contributes significantly to our understanding of mineral exploration processes and offers new avenues for future research and practical applications.

Improved Cycling Stability of LFP by W-Ti Co-Doping Strategy for Li-Ion Batteries

Olivine-type lithium iron phosphate (LFP) is used widely as a cathode material with excellent cycling stability, thermal stability, and low cost for lithium-ion batteries in power vehicles and energy storage. However, it has inherent drawbacks that limit its further development, such as low electronic conductivity and lithium ion diffusion rate. Here, secondary spherical particles LFP-W/Ti@C were synthesized using a simple sanding and spray drying method. The pyrolysis of glucose forms a uniform and dense amorphous carbon on the surface of LFP, and the constructed three-dimensional conductive network accelerates the transfer of electrons and ions while mitigating the volume expansion during the lithiation-delithiation process. In addition, the synergistic co-doping of W/Ti achieves nanosizing of primary particles with more active sites providing locations for lithium ions storage, while reducing polarization and internal resistance and enhancing the diffusion kinetics of lithium ion. The LFP-W/Ti@C obtained after optimization still has a discharge capacity of 107.7 mAh g−1 (with a cycle retention rate of up to 100%) after 500 cycles at 5 C. This simple W/Ti co-doping strategy provides excellent rate performance and shows great potential for fast charging in electric vehicles.

Plane-controlled growth strategy improves electrochemical performance of cobalt-free LiNi0.9Mn0.1O2 cathode

The ultra-high nickel-layered cathodes (Ni ​≥ ​90 ​%) has garnered significant attention due to its high specific capacity. However, the widespread application of ultra-high nickel-layered cathodes still suffers limitation by structural instability and poor rate performance. Herein, a crystal-face-induced strategy is proposed to enhance rate and cycling performances of the electrode by constructing rapid Li+ diffusion channel and reducing internal grain boundaries of secondary particles. The crystal-face-induced strategy facilitates the growth of {010} lattice plane. Highly exposed {010} planes provide wide-open and unobstructed channels for Li+ deintercalation/intercalation, enhances the electrode diffusion kinetics, and thus improves the electrode rate performance. In addition, this strategy promotes the primary particle growth, reduces the grain boundaries of secondary particles and mitigates the electrode/electrolyte interface side reactions, enhancing the structural stability and cycling life of the electrode. Accordingly, the modified sample achieved a reversible specific capacity of 198.3 ​mAh g−1 at 1 ​C (1 ​C ​= ​180 ​mA ​g−1) and maintained a capacity retention rate of 88.5 % after 100 cycles, higher than that of the original sample (73.6 %, 146 ​mAh g−1). At the high rate of 5 ​C, it can maintain a high specific capacity of 178 ​mAh g−1 (capacity retention rate of 99 %) after 150 cycles. This work is a leap in ultra-high nickel-layered cathodes development and provides insights into the design of electrode materials for other batteries.

Effect of process conditions on the performance of LiNi0.815Co0.15Al0.035O2 positive electrode material powder synthesized by hydrothermal approach

LiNi0.815Co0.15Al0.035O2 (NCA) lithium-ion battery cathode material was prepared using a hydrothermal approach. XRD and SEM analyzed the crystal parameters and powder morphology of the cathode material. The results show that the nickel cobalt precursor exhibits a petal-like morphology, and the nanoneedle primary particles are randomly distributed. Accompanied by the increase in calcination temperature and time, the peak intensity ratio of I003/I104 tends to decrease and then increase. The peak intensity ratio reached a maximum when the NCA sample calcined at 750°C for 8 h, indicating the lowest extent of Li/Ni mixing and the best electrochemical performance of the positive electrode material.

Sublimation and oxidation measurements of graphite and carbon black at high temperatures in a shock tube using absorption imaging and thermal emission

Surface mass loss rates due to sublimation and oxidation at temperatures of 3000–7000 K have been measured in a shock tube for graphite and carbon black (CB) particles. Diagnostics are presented for measuring surface mass loss rates by diffuse backlit illumination extinction imaging and thermal emission. The surface mass loss rate is found by regression fitting extinction and emission signals with an independent spherical primary particle assumption. Measured graphite sublimation and oxidation rates are reported to be an order of magnitude greater than CB sublimation and oxidation rates. It is speculated that the difference between CB and graphite surface mass loss rates is largely due to the primary particle assumption of the presented technique which misrepresents the effective surface area of an aggregate particle where primary particles overlap and shield inner particles. Measured sublimation rates are compared to sublimation models in the literature, and it is seen graphite shows fair agreement with the models while CB underestimates, likely a result of the particle shielding affect not being considered in the sublimation model.

Soils on Recent Tephra of the Somma–Vesuvius Volcanic Complex, Italy

The Somma–Vesuvius volcanic complex emitted huge quantities of volcanic materials over a period from before 18,300 years BP to 1944. The activity during the last period, from post-AD 1631 to 1944, primarily produced lava and pyroclastics via effusive and strombolian eruptions. We investigated the pedogenesis on rocks formed from post-AD 1631 to 1944, occurring on the slopes of Mt. Vesuvius up to Gran Cono Vesuviano and in the northern valley separating Vesuvius from the older Mt. Somma edifice. Pertinent morphological, physical, chemical, and mineralogical (XRD and FT-IR) soil properties were studied. The results indicated the existence of thin and deep stratified soils on lava, as well as the presence of loose detritic covers formed via pyroclastic emplacement and redistribution. The soils showed minimal profile differentiation, frequently with layering recording the episodic addition of sediments. We found that the dominant coarse size of primary mineral particles was preserved, and there was a low level of clay production. The main mineralogical assemblage present in sands also persisted in clays, indicating the physical breaking of the parent material. Chemical weathering produced mineral modifications towards the active forms of Al and Fe and was also attested in selected soils by glass alteration, allophane production, and the presence of analcime in clay as a secondary product from leucite. The differences in glass alteration and analcime production found in the selected soils on lava were related to soil particle size and soil thickness. Concerning the youngest soil present on Gran Cono Vesuviano, other factors, such as the substratum’s age and site elevation, appeared to be implicated.

Magnetic Field-Optimized Paramagnetic Nanoprobe for T2/T1 Switchable Histopathological-Level MRI.

Traditional magnetic resonance imaging (MRI) contrast agents (CAs) are a type of "always on" system that accelerates proton relaxation regardless of their enrichment region. This "always on" feature leads to a decrease in signal differences between lesions and normal tissues, hampering their applications in accurate and early diagnosis. Herein, we report a strategy to fabricate glutathione (GSH)-responsive one-dimensional (1-D) manganese oxide nanoparticles (MONPs) with improved T2 relaxivities and achieve effective T2/T1 switchable MRI imaging of tumors. Compared to traditional contrast agents with high saturation magnetization to enhance T2 relaxivities, 1-D MONPs with weak Ms effectively increase the inhomogeneity of the local magnetic field and exhibit obvious T2 contrast. The inhomogeneity of the local magnetic field of 1-D MONPs is highly dependent on their number of primary particles and surface roughness according to Landau-Lifshitz-Gilbert simulations and thus eventually determines their T2 relaxivities. Furthermore, the GSH responsiveness ensures 1-D MONPs with sensitive switching from the T2 to T1 mode in vitro and subcutaneous tumors to clearly delineate the boundary of glioma and metastasis margins, achieving precise histopathological-level MRI. This study provides a strategy to improve T2 relaxivity of magnetic nanoparticles and construct switchable MRI CAs, offering high tumor-to-normal tissue contrast signal for early and accurate diagnosis.

Comparison Study of a Thermal-Driven Microstructure in a High-Ni Cathode for Lithium-Ion Batteries: Critical Calcination Temperature for Polycrystalline and Single-Crystalline Design.

High-Ni layered oxide cathodes are promising candidates for lithium-ion batteries due to their high energy density. However, their cycle stability is compromised by the poor mechanical durability of the particle microstructure. In this study, we investigate the impact of the calcination temperature on microstructural changes, including primary particle growth and pore evolution, using LiNi0.88Mn0.08Co0.04O2 (N884), with an emphasis on the critical calcination temperature for polycrystalline and single-crystal designs in high-Ni cathodes. As the calcination temperature increases, the primary particles undergo a rectangular growth pattern while the pore population decreases. Beyond a certain critical temperature (in this case, 850 °C), a sudden increase in primary particle size and a simultaneous rapid reduction in the pore population are observed. This sudden microstructure evolution leads to poor cycle retention in N884. In contrast, single-crystal particles, free of grain boundaries, synthesized at this critical temperature exhibit superior cycle retention, underscoring the significance of microstructural design over crystalline quality for achieving long-term cyclability. Our study sheds light on the interplay between calcination temperature and microstructural evolution, proposing the critical temperature as a key criterion for single-crystal synthesis.

Preoxidation and Prilling Combined with Doping Strategy to Build High-Performance Recycling Spent LiFePO4 Materials.

Direct regeneration has gained much attention in LiFePO4 battery recycling due to its simplicity, ecofriendliness, and cost savings. However, the excess carbon residues from binder decomposition, conductive carbon, and coated carbon in spent LiFePO4 impair electrochemical performance of direct regenerated LiFePO4. Herein, we report a preoxidation and prilling collaborative doping strategy to restore spent LiFePO4 by direct regeneration. The excess carbon is effectively removed by preoxidation. At the same time, prilling not only reduces the size of the primary particles and shortens the diffusion distance of Li+ but also improves the tap density of the regenerated materials. Besides, the Li+ transmission of the regenerated LiFePO4 is further improved by Ti4+ doping. Compared with commercial LiFePO4, it has excellent low-temperature performance. The collaborative strategy provides a new insight into regenerating high-performance spent LiFePO4.

Origins and Importance of Intragranular Cracking in Layered Lithium Transition Metal Oxide Cathodes.

Li-ion batteries have a pivotal role in the transition toward electric transportation. Ni-rich layered transition metal oxide (LTMO) cathode materials promise high specific capacity and lower cost but exhibit faster degradation compared with lower Ni alternatives. Here, we employ high-resolution electron microscopy and spectroscopy techniques to investigate the nanoscale origins and impact on performance of intragranular cracking (within primary crystals) in Ni-rich LTMOs. We find that intragranular cracking is widespread in charged specimens early in cycle life but uncommon in discharged samples even after cycling. The distribution of intragranular cracking is highly inhomogeneous. We conclude that intragranular cracking is caused by local stresses that can have several independent sources: neighboring particle anisotropic expansion/contraction, Li- and TM-inhomogeneities at the primary and secondary particle levels, and interfacing of electrochemically active and inactive phases. Our results suggest that intragranular cracks can manifest at different points of life of the cathode and can potentially lead to capacity fade and impedance rise of LTMO cathodes through plane gliding and particle detachment that lead to exposure of additional surfaces to the electrolyte and loss of electrical contact.