Natasha A. Chernova

Layered vanadium and molybdenum oxides: batteries and electrochromics

The layered oxides of vanadium and molybdenum have been studied for close to 40 years as possible cathode materials for lithium batteries or electrochromic systems. The highly distorted metal octahedra naturally lead to the formation of a wide range of layer structures, which can intercalate lithium levels exceeding 300 Ah/kg. They have found continuing success in medical devices, such as pacemakers, but many challenges remain in their application in long-lived rechargeable devices. Their high-energy storage capability remains an encouragement to researchers to resolve the stability concerns of vanadium dissolution and the tendency of lithium and vanadium to mix changing the crystal structure on cycling the lithium in and out. Nanomorphologies have enabled higher reactivities to be obtained for both vanadium and molybdenum oxides, and with the latter show promise for electrochromic displays.

Conversion Reaction Mechanisms in Lithium Ion Batteries: Study of the Binary Metal Fluoride Electrodes

Materials that undergo a conversion reaction with lithium (e.g., metal fluorides MF(2): M = Fe, Cu, ...) often accommodate more than one Li atom per transition-metal cation, and are promising candidates for high-capacity cathodes for lithium ion batteries. However, little is known about the mechanisms involved in the conversion process, the origins of the large polarization during electrochemical cycling, and why some materials are reversible (e.g., FeF(2)) while others are not (e.g., CuF(2)). In this study, we investigated the conversion reaction of binary metal fluorides, FeF(2) and CuF(2), using a series of local and bulk probes to better understand the mechanisms underlying their contrasting electrochemical behavior. X-ray pair-distribution-function and magnetization measurements were used to determine changes in short-range ordering, particle size and microstructure, while high-resolution transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS) were used to measure the atomic-level structure of individual particles and map the phase distribution in the initial and fully lithiated electrodes. Both FeF(2) and CuF(2) react with lithium via a direct conversion process with no intercalation step, but there are differences in the conversion process and final phase distribution. During the reaction of Li(+) with FeF(2), small metallic iron nanoparticles (<5 nm in diameter) nucleate in close proximity to the converted LiF phase, as a result of the low diffusivity of iron. The iron nanoparticles are interconnected and form a bicontinuous network, which provides a pathway for local electron transport through the insulating LiF phase. In addition, the massive interface formed between nanoscale solid phases provides a pathway for ionic transport during the conversion process. These results offer the first experimental evidence explaining the origins of the high lithium reversibility in FeF(2). In contrast to FeF(2), no continuous Cu network was observed in the lithiated CuF(2); rather, the converted Cu segregates to large particles (5-12 nm in diameter) during the first discharge, which may be partially responsible for the lack of reversibility in the CuF(2) electrode.

Some transition metal (oxy)phosphates and vanadium oxides for lithium batteries

Iron and vanadium oxides have a rich structural chemistry when combined with phosphate groups; the transition metal most commonly in an octahedral coordination. The inductive effect increases the potential difference between Fe3+/Fe2+ and Li/Li+ couples in phosphate lattices relative to the pure iron oxides; a similar behavior is found for the corresponding vanadium compounds. Of the iron phosphates, the olivine phase LiFePO4 has high thermal and chemical stability, even when lithium-free; the challenges of low electronic conductivity are being overcome, but data is lacking on the true lithium diffusion behavior. The all-ferric lipscombite-type phase, Fe1.33PO4OH, shows the highest capacity of the iron phosphates for lithium intercalation. The e-VOPO4 material, formed by the oxidative de-intercalation of protons from H2VOPO4, can reversibly react with two lithium atoms in two steps. The face- and edge-sharing transition metal octahedra lead to a range of interesting and structurally revealing magnetic interactions. A number of vanadium oxide phases are known, with those containing VO6 octahedra showing the greatest stability when undergoing redox reactions. Such structures have been synthesized using xerogel, hydrothermal and electrochemical methods. The double-sheet delta structures show reversible lithium intercalation of up to one lithium ion per vanadium, leading to the highest storage capacities. However, the large potential width of discharge and the apparent low reaction rates will minimize their use unless improved.

The synthesis, characterization and electrochemical behavior of the layered LiNi0.4Mn0.4Co0.2O2 compound

The mixed transition metal layered compound, LiNi0.4Mn0.4Co0.2O2, with the α-NaFeO2 layer structure has been synthesized and characterized. The optimum temperature of synthesis was found to be 800–900 °C. Rietveld refinement showed that cobalt suppresses transition metal ion migration into the Li sites whereas nickel promotes the migration. XPS analysis shows that the Co and about 20% of the Ni and Mn are in the 3+ oxidation state, while 80% of the Ni and Mn are in the 2+ and 4+ oxidation states, respectively. LiNi0.4Mn0.4Co0.2O2 shows Curie–Weiss paramagnetic behavior above 150 K, and the value of the Curie constant is consistent with the above oxidation states. In lithium electrochemical cells the composition LiNi0.4Mn0.4Co0.2O2 gave the highest reversible capacity among the studied compositions. It shows excellent rate capability, giving reversible capacities ranging from 180 to 155 mA h g−1 at current densities from 0.1 to 2.0 mA cm−2.

Linking Local Environments and Hyperfine Shifts: A Combined Experimental and Theoretical 31P and 7Li Solid–State NMR Study of Paramagnetic Fe(III) Phosphates

Iron phosphates (FePO(4)) are among the most promising candidate materials for advanced Li-ion battery cathodes. This work reports upon a combined nuclear magnetic resonance (NMR) experimental and periodic density functional theory (DFT) computational study of the environments and electronic structures occurring in a range of paramagnetic Fe(III) phosphates comprising FePO(4) (heterosite), monoclinic Li(3)Fe(2)(PO(4))(3) (anti-NASICON A type), rhombohedral Li(3)Fe(2)(PO(4))(3) (NASICON B type), LiFeP(2)O(7), orthorhombic FePO(4)·2H(2)O (strengite), monoclinic FePO(4)·2H(2)O (phosphosiderite), and the dehydrated forms of the latter two phases. Many of these materials serve as model compounds relevant to battery chemistry. The (31)P spin-echo mapping and (7)Li magic angle spinning NMR techniques yield the hyperfine shifts of the species of interest, complemented by periodic hybrid functional DFT calculations of the respective hyperfine and quadrupolar tensors. A Curie-Weiss-based magnetic model scaling the DFT-calculated hyperfine parameters from the ferromagnetic into the experimentally relevant paramagnetic state is derived and applied, providing quantitative finite temperature values for each phase. The sensitivity of the hyperfine parameters to the composition of the DFT exchange functional is characterized by the application of hybrid Hamiltonians containing admixtures 0%, 20%, and 35% of Fock exchange. Good agreement between experimental and calculated values is obtained, provided that the residual magnetic couplings persisting in the paramagnetic state are included. The potential applications of a similar combined experimental and theoretical NMR approach to a wider range of cathode materials are discussed.

Comparative Study of the Capacity and Rate Capability of LiNi y Mn y Co1–2y O2 (y = 0.5, 0.45, 0.4, 0.33)

An unresolved question for the layered oxides is: what is the optimum value of y in the formula LiNi{sub y}Mn{sub y}Co{sub 1-2y}O{sub 2} for energy storage at moderate reaction rates? Here we report a systematic study of the specific capacity, rate capability and cycle life of Li{sub x}Ni{sub y}Mn{sub y}Co{sub 1-2y}O{sub 2}(y = 0.5, 0.45, 0.4, and 0.333). The voltage of the Li/y = 0.333 couple crosses over those of lower cobalt content for x 0.333 when charging above 4 V. Overall the y = 0.4 material has the optimum properties, having the highest theoretical capacity, less of the expensive cobalt and yet rate capabilities and capacity retention comparable to the y = 0.333 material.

An organic coprecipitation route to synthesize high voltage LiNi0.5Mn1.5O4.

High-voltage cathode material LiNi0.5Mn1.5O4 has been prepared with a novel organic coprecipitation route. The as-prepared sample was compared with samples produced through traditional solid state method and hydroxide coprecipitation method. The morphology was observed by scanning electron microscopy, and the spinel structures were characterized by X-ray diffraction and Fourier transform infrared spectroscopy. Besides the ordered/disordered distribution of Ni/Mn on octahedral sites, the confusion between Li and transition metal is pointed out to be another important factor responsible for the corresponding performance, which is worthy further investigation. Galvanostatic cycles, cyclic voltammetry, and electrochemical impedance spectroscopy are employed to characterize the electrochemical properties. The organic coprecipitation route produced sample shows superior rate capability and stable structure during cycling.

Study of the transition metal ordering in layered Na(x)Ni(x/2)Mn(1-x/2)O2 (2/3 ≤ x ≤ 1) and consequences of Na/Li exchange.

A series of layered oxides within the Na(x)Ni(ix/2)Mn(1-x/2)O2 (2/3 ≤ x ≤ 1) system were synthesized by classical solid-state methodologies. A study of their long and short-range structure was undertaken by combining X-ray diffraction and NMR spectroscopy. A transition from P2 to O3 stacking was observed at x > 0.8 when samples were made at 900 °C, which was accompanied by disordering of ions in the transition metal layer. The magnetic properties of the materials were consistent with this picture of ordering, with all samples showing antiferromagnetic character. At x = 2/3, competition between a P2 and a P3 structure, with different degrees of transition metal ordering, was found depending on the synthesis temperature. Na/Li exchange led to structures with octahedral or tetrahedral coordination of the alkali metal, and Li/Ni crystallographic exchange in the resulting O3 phases. The transition from alkali metal prismatic coordination to octahedral/tetrahedral coordination involves [TMO6]∞ layer shearing that induces some structural disorder through the formation of stacking faults.

What can we learn about battery materials from their magnetic properties

Electrode materials for Li-ion batteries should combine electronic and ionic conductivity, structural integrity, and safe operation over thousands of lithium insertion and removal cycles. The quest for higher energy density calls for better understanding of the redox processes, charge and mass transfer occurring upon battery operation. A number of techniques have been used to characterize long-range and local structure, electronic and ionic transport in bulk of active materials and at interfaces, with an ongoing move toward in situ techniques determining the changes as they happen. This paper reviews several representative examples of using magnetic properties toward understanding of Li-ion battery materials with a notion to highlight the intimate connection between the magnetism, electronic and atomic structure of solids, and to demonstrate how this connection has been used to reveal the fine electronic and atomic details related to the electrochemical performance of the battery materials.

Core-Shell Structured Magnetic Ternary Nanocubes

We report a novel core-shell-structured ternary nanocube of MnZn ferrite synthesized by controlling the reaction temperature and composition in the absence of conventionally used reducing agents. The highly monodispersed core-shell structure consists of an Fe(3)O(4) core and an MnZn Ferrite shell. The observation of a Moiré pattern indicates that the core and the shell are two highly crystalline materials with slightly different lattice constants that are rotated relative to each other by a small angle. The ternary core-shell nanocubes display magnetic properties regulated by a combination of the core-shell composition and exhibit an increased coercivity and field-cooled/zero-field-cooled characteristics drastically different from those of regular MnZn ferrite nanoparticles. The ability to engineer the spatial nanostructures of ternary magnetic nanoparticles in terms of shape and composition offers atomic-level versatility in fine-tuning the nanoscale magnetic properties.