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Thermal decomposition characteristics of sodium superoxide, sodium peroxide, and lithium peroxide and magnetic susceptibility of calcium superoxide
The preparation and evaluation of zinc orthotitanate and of several new pigments and the environmental testing and evaluation of these pigments and of coatings made from them constitute the bulk of the work accomplished. New pigments were prepared and EPR spectra of pigments and their precursor compounds studied. Results of extensive testing of commercially-available, strippable, protective coatings are reported; Owens-Illinois 650 glass resin has been stabilized against progressive mechanical failures; and definite improvements have been noted. A zinc oxide pigmented lithium silicate paint has demonstrated very good ultraviolet stability.
Structural information of special interest to crystal growers and device physicists is now available from high resolution monochromatic synchrotron diffraction imaging (topography). In the review, the importance of superior resolution in momentum transfer and in space is described, and illustrations are taken from a variety of crystals: gallium arsenide, cadmium telluride, mercuric iodide, bismuth silicon oxide, and lithium niobate. The identification and understanding of local variations in crystal growth processes are shown. Finally, new experimental opportunities now available for exploitation are indicated.
Efficient second-harmonic conversion of the 1064-nm output of a diode-pumped CW single-frequency Nd:YAG laser to 532 nm was obtained by frequency locking the laser to a monolithic ring resonator constructed of magnesium-oxide-doped lithium niobate. The conversion efficiency from the fundamental to the second harmonic was 65 percent. Two hundred milliwatts of CW single-frequency 532-nm light were produced from 310 mW of power of 1064-nm light. This represents a conversion efficiency of 20 percent from the 1-W diode laser used to pump the Nd:YAG laser to single-frequency 532-nm output. No signs of degradation were observed for over 500 h of operation.
A cathode active material precursor for a lithium metal oxide is provided. The cathode active material precursor comprises a metal-containing oxyhydroxide. The metal-containing oxyhydroxide comprises nickel and an additional metal. At least 50 mol. % of the nickel of the metal-containing oxyhydroxide has an oxidation state of +3. A method of forming a cathode active material precursor is also provided. The method comprises combining a nickel-containing compound, an additional metal-containing compound, an oxidizing agent, and a solvent to form a solution. The method further comprises exposing the solution to heat at a temperature of from about 30° C. to about 90° C. to form a precipitate comprising the metal-containing oxyhydroxide.
A method for relithiating cathode material from spent lithium-based batteries, the method comprising: (i) mixing delithiated cathode material and a lithium salt with an ionic liquid in which the lithium salt is at least partially soluble to form an initial mixture; (ii) heating the initial mixture to a temperature of 100° C. to 300° C. to result in relithiation of the delithiated cathode material; and (iii) separating the ionic liquid from the relithiated cathode material; wherein, in embodiments, the cathode material is a lithium metal oxide, wherein the metal is selected from the group consisting of Ni, Co, Fe, Mn, Al, Zr, Ti, Nb, and combinations thereof, or wherein the cathode material has the formula LiNi x Mn y Co z O 2 , wherein x>0, y>0, z>0, and x+y+z=1; wherein, in some embodiments, the ionic liquid has a nitrogen-containing cationic portion, such as an imidazolium ionic liquid.
An active cathode material containing particles with a core containing a lithium transition metal oxide, each core at least partially encapsulated by a layer including the lithium transition metal oxide and dopant cation; and an outer layer containing metal oxide; wherein the dopant cation is selected from the group consisting of Al, Ti, Sn, Mg, Zr, Cu, Fe, Ca, W, Ga, Sc, Y, La, Hf, V, In, Nb, Ta, and any combination of two or more thereof; and the dopant cation is present in an amount of 10 wt. % or less of the particle.
A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.
Developing a materials perspective of how to control the degradation and negative impact of complex metal oxides requires an integrated understanding of how these nanomaterials transform in the environment and interact with biological systems. Doping with aluminum is known to stabilize oxide materials, but has not been assessed cohesively from synthesis to environmental fate and biological impact. In the present study, the influence of aluminum doping on metal ion release from transition metal oxides was investigated by comparing aqueous transformations of lithium nickel cobalt aluminum oxide (LiNi 0.82 Co 0.15 Al 0.03 O 2 ; NCA) and lithium nickel cobalt oxide (LiNi 0.80 Co 0.20 O 2 ; NC) nanoparticles and by calculating the energetics of metal release using a density functional theory (DFT) and thermodynamics method. Two model environmental organisms were used to assess biological impact, and metal ion release was compared for NCA and NC nanoparticles incubated in their respective growth media: moderately hard reconstituted water (MHRW) for the freshwater invertebrate Daphnia magna (D. magna) and minimal growth medium for the Gram-negative bacterium Shewanella oneidensis MR-1 (S. oneidensis). Further, the amount of metal ions released was reduced for NCA compared to NC in MHRW, which correlated to changes in the modeled energetics of release upon Al substitution in the lattice. In minimal medium, metal ion release was approximately an order of magnitude higher compared to MHRW and was similar to the stoichiometry of the bulk nanoparticles for both NCA and NC. Interpretation of the release profiles and modeling indicated that the increase in total metal ion release and the reduced influence of Al doping arises from lactate complexation of metal ions in solution. The relative biological impacts of NC and NCA exposure for both S. oneidensis and D. magna were consistent with the metal release trends observed for minimal medium and MHRW, respectively. Together, these results demonstrate how a combined experimental and computational approach provides valuable insight into the aqueous transformations and biological impacts of complex metal oxide nanoparticles.
Lithium vanadate (Li 3 VO 4 ) has garnered considerable attention as an alternative negative electrode material for non-aqueous lithium-ion batteries due to its high capacity, energy efficiency, and stable discharge voltage. Nonetheless, the Li 3 VO 4 material displays a low rate capability, attributed mainly to its poor intrinsic electronic conductivity. Here, in this study, we report the synthesis of lithium niobate LiNbO 3 -coated Li 3 VO 4 (LVO@LNO) using a one-pot sol-gel method. The resulting LVO@LNO demonstrates a high reversible capacity of approximately 530 mAh/g, which is more than double that of free Li 3 VO 4 . To explore the effect of the LNO coating process on the morphological and structural properties, Raman, XRD, operando XRD, XPS, SEM and HTEM analyses were conducted. To explain the enhancement of electronic conductivity in our modified material after a LiNbO 3 coating, we conducted an Ex-Situ electrochemical impedance (EIS) and Density Functional Theory (DFT) computational study. Additionally, we designed a full cell utilizing a 1 wt% LNO-coated LVO anode and NMC-811 cathode. The cell yielded an output voltage of approximately 2.8 V with a high initial specific capacity of 350 mAh/g versus to the anode, at 1C with a capacity retention of 85 % after 100 cycles.
In this study, we synthesized spinel high-entropy oxide (HEO) (Cr0.2Mn0.2Co0.2Ni0.2Zn0.2)3O4 nanoparticles by a simple solution combustion method. These particles were investigated for their performance as anodes in lithium-ion batteries. The reversible capacity is 132 mAh·g−1 after 100 cycles at a current density of 100 mA·g−1, 107 mAh·g−1 after 1000 cycles at a current density of 1 A g−1, and 96 mAh·g−1 rate capacity at a high current density of 2 A g−1. The outstanding cycle stability under high current densities and remarkable rate performance can be attributed to the stable structure originating from the high entropy of the material.
Electrode-electrolyte reactivity (EER) and particle cracking (PC) are considered two main causes of capacity fade in high-nickel layered oxide cathodes in lithium-based batteries. However, whether EER or PC is more critical remains debatable. Herein, the fundamental correlation between EER and PC is systematically investigated with LiNiO 2 (LNO), the ultimate cobalt-free lithium layered oxide cathode. Specifically, EER is found more critical than secondary particle cracking (SPC) in determining the cycling stability of LNO; EER leads to primary particle cracking, but mitigates SPC due to the inhibition of H2-H3 phase transformation. Two surface degradation pathways are identified for cycled LNO under low and high EERs. A common blocking surface reconstruction layer (SRL) containing electrochemically-inactive Ni 3 O 4 spinel and NiO rock-salt phases is formed on LNO in an electrolyte with a high EER; in contrast, an electrochemically-active SRL featuring regions of electron- and lithium-ion-conductive LiNi 2 O 4 spinel phase is formed on LNO in an electrolyte with a low EER. These findings unveil the intrinsic degradation pathways of LNO cathode and are foreseen to provide new insights into the development of lithium-based batteries with a minimized EER and a maximized service life.
The performance of single-ion conductors is highly sensitive to the material’s defect chemistry. Tuning these defects is limited for solid-state reactions as they occur at particle–particle interfaces, which provide a complex evolving energy landscape for atomic rearrangement and product formation. In this report, we investigate the (1) order of addition and (2) lithium precursor decomposition temperature and their effect on the synthesis and grain boundary conductivity of the perovskite lithium lanthanum titanium oxide (LLTO). We use an intimately mixed sol–gel, a solid-state reaction of Li precursor + La 2 O 3 + TiO 2 , and Li precursor + amorphous La 0.57 TiO x as different chemical routes to change the way in which the elements are brought together. The results show that the perovskite can accommodate a wide range of Li deficiencies (upward of 50%) while maintaining the tetragonal LLTO structure, indicating that X-ray diffraction (XRD) is insufficient to fully characterize the chemical nature of the product (i.e., Li-deficient LLTO may behave differently than stoichiometric LLTO). Variations in the relative intensities of different reflections in XRD suggest variations in the La ordering within the crystal structure between synthesis methods. Furthermore, the choice of the precursor and the order of addition of the reactants lower the time required to form a pure phase. Density functional theory calculations of the formation energy of possible reaction intermediates support the hypothesis that a greater thermodynamic driving force to form LLTO leads to a greater LLTO yield. Here, the retention of lithium is correlated with the thermal decomposition temperature of the Li precursor and the starting material mixing strategy. Taking the results together suggests that cations that share a site with Li should be mixed early to avoid ordering. Such cation ordering inhibits Li motion, leading to higher Li ion resistance.
Layered, nickel-rich lithium transition metal oxides have emerged as leading candidates for lithium-ion battery (LIB) cathode materials. High-performance applications for nickel-rich cathodes, such as electric vehicles and grid-level energy storage, demand electrodes that deliver high power without compromising cell lifetimes or impedance. Nanoparticle-based nickel-rich cathodes seemingly present a solution to this challenge due to shorter lithium-ion diffusion lengths compared to incumbent micrometer-scale active material particles. However, since smaller particle sizes imply that surface effects become increasingly important, particle surface chemistry must be well characterized and controlled to achieve robust electrochemical properties. Moreover, residual surface impurities can disrupt commonly used carbon coating schemes, which result in compromised cell performance. Using x-ray photoelectron spectroscopy, here we present a detailed characterization of the surface chemistry of LiNi0.8Al0.15Co0.05O2 (NCA) nanoparticles, ultimately identifying surface impurities that limit LIB performance. With this chemical insight, annealing procedures are developed that minimize these surface impurities, thus improving electrochemical properties and enabling conformal graphene coatings that reduce cell impedance, maximize electrode packing density, and enhance cell lifetime fourfold. Overall, this work demonstrates that controlling and stabilizing surface chemistry enables the full potential of nanostructured nickel-rich cathodes to be realized in high-performance LIB technology.
High-energy density lithium-rich layered oxides are among the most promising candidates for next-generation energy storage. Unfortunately, these materials suffer from severe electrochemical degradation that includes capacity loss and voltage decay during long-term cycling. Present research efforts are primarily focused on understanding voltage decay phenomena while origins for capacity degradation have been largely ignored. Here, we thoroughly investigate causes for electrochemical performance decline with an emphasis on capacity loss in the lithium-rich layered oxides, as well as reaction pathways and kinetics. Advanced synchrotron-based X-ray two-dimensional and three-dimensional imaging techniques are combined with spectroscopic and scattering techniques to spatially visualize the reactivity at multiple length-scales on lithium- and manganese-rich layered oxides. These methods provide direct evidence for inhomogeneous manganese reactivity and ionic nickel rearrangement. Coupling deactivated manganese with nickel migration provides sluggish reaction kinetics and induces serious structural instability in the material. Our findings provide new insights and further understanding of electrochemical degradation, which serve to facilitate cathode material design improvements.
Metal oxides have been actively explored as promising conversion-type electrode materials for lithium ion batteries due to high deliverable capacity but still notorious for poor cyclability, capacity fading, voltage hysteresis, etc. Yet, the fundamental reason for the undesirable properties of metal oxides behind the repetitive conversion process is still obscure. In this work, we take advantage of synchrotron X-ray techniques as well as transmission electron microscopy to monitor the structural changes during both conversion (lithiation) and reconversion (delithiation) reactions. Difference in diffusion rates of lithium and metal plays a decisive role in determining the reaction pathway. We find lithium accommodation and extraction occur via different reaction routes: lithiation follows a kinetically driven way while delithiation adopts a route close to the thermodynamic ground state path. Thermodynamic structural evolution features the formation of an intermediate phase of Li-Metal (M)-O, suggesting lithium removal accompanies with the Li/M ionic exchange and rearrangement of oxygen framework. The slow diffusion of metal ions and the high kinetic and energy barrier for dissociating the intermediate phase are mainly responsible for uncompleted reconversion reaction, evidenced by remaining Li-M-O phase at the end of charge. Imperfect reconversion reaction eventually limits the utilization of lithium ions over the repeated cycling. Furthermore, this work sheds light on structural changes occurring at metal oxides during both conversion and reconversion processes, which is strongly linked with the performances of conversion-type materials in applications.
Stability of perovskite solar cells (PSCs) under light, heat, humidity and their combinations have been notably improved recently. However, PSCs have poor reverse-bias stability that limits their real-world application. Here we report a systematic study on the degradation mechanisms of p-i-n structure PSCs under reverse bias. The oxidation of iodide by injected holes at the cathode side initialize the reverse-bias-induced degradation, then the generated neutral iodine oxidizes metal electrode such as copper, followed by drift of Cu+ into perovskites and its reduction by injected electrons, resulting in localized metallic filaments and thus device breakdown. A reinforced barrier with combined lithium fluoride, tin oxide and indium tin oxide at the cathode side reduces device dark current and avoids the corrosion of Cu0. It dramatically increases breakdown voltage to above -20 V and improved the T90 lifetime of PSCs to ~1,000 h under -1.6 V. The modified minimodule also maintained over 90% of its initial performance after 720 h of shadow tests.