The Origins of the Rate Enhancement in LiNi0.4Co0.2-yAlyMn0.4O2 (0<y<_0.2) Cathode Materials

Recently, much research has been directed towards finding a replacement cathode material for LiCoO{sub 2} combining high performance with lower cost and toxicity. One promising candidate material is the mixed transition metal oxide LiNi{sub 0.4}Co{sub 0.2}Mn{sub 0.4}O{sub 2}, which delivers 180 mAh/g below 4.4 V versus Li/Li{sup +} (1, 2). However, in this material, there is 4% anti-site cation mixing, which hinders the mobility of lithium within the lattice, adversely affecting its rate performance in lithium batteries. Ongoing work in our lab has shown that partial or full substitution of cobalt with aluminum, LiNi{sub 0.4}Co{sub 0.2}Mn{sub 0.4}O{sub 2} (0 &lt; y {le} 0.2), can lead to significant improvements in rate performance (3). In particular, LiNi{sub 0.4}Co{sub 0.2}Mn{sub 0.4}O{sub 2} shows greatly improved rate capability with almost no sacrifice in the overall capacity delivered at low rates between 2.0 and 4.3V (Figure 1). The smaller ionic radius of Al{sup 3+} in octahedral coordination (0.535 {angstrom}) compared to Li{sup +} (0.76 {angstrom}) creates a strong driving force for the formation of a more lamellar structure in the aluminum containing materials (4, 5). XRD experiments and subsequent Rietveld refinement (Figure 2) reveal a significant decrease in anti-site defect concentration upon aluminum substitution, dropping from {approx}4% at y=0 to {approx}2.5% at y=0.2. Concurrently, there is an increase in the lithium slab dimension from 2.6 {angstrom} to 2.63 {angstrom}. This expansion allows for a reduced activation energy and improved lithium diffusivity through the crystal lattice (6). Interestingly, the pressed pellet conductivities of Al-substituted compounds are lower than that of the parent as determined by AC impedance measurements. This lends further credence to the hypothesis that structural effects resulting in improved lithium diffusivity are responsible for the rate enhancement, rather than changes in the electronic structure. Further experiments to understand the effect of structural changes induced by Al substitution on the transport properties are underway in this laboratory. The changes in electronic conductivity and the chemical diffusion coefficient of lithium as determined by pressed pellet conductivities and GITT experiments will be discussed. Further refinement of cation ordering and crystal structure parameters as determined from neutron diffraction and XANES experiments will also be presented

Electrode Materials with the Na0.44MnO2 Structure: Effect ofTitanium Substitution on Physical and Electrochemical Properties

The physical and electrochemical properties of LixMnO2 and LixTi0.11Mn0.89O2 synthesized from precursors made by glycine-nitrate combustion (GNC) and solid-state synthesis methods (SS) are examined in this paper. The highest specific capacities in lithium cells are obtained for SS-LixMnO2 electrodes at low current densities, but GNC-LixTi0.11Mn0.89O2 electrodes show the best high rate performance. These results can be explained by changes in the voltage characteristics and differences in the particle morphologies induced by the Ti-substitution and synthesis method. Ti-substitution also results in a decrease in the electronic conductivity, but greatly improves the thermal properties and imparts dissolution resistance to the electrode. For these reasons, it is preferable to use LixTi0.11MnO0.89O2 in lithium battery configurations rather than LixMnO2. Suggestions for improving the electrochemical performance of the Ti-substituted variant are given based on the results described herein

Characterization and Electrochemical Performance of SubstitutedLiNi0.4Co0.2-yAlyMn0.4O2 (0&lt;_y&lt;_0.2) Cathode Materials

A complete series of LiNi0.4Co0.2-yAlyMn0.4O2 (0&lt;_y&lt;_0.2) materials have been synthesized and investigated as cathode materials for lithium ion batteries. When cycled between 2.0 and 4.3 V vs. Li/Li+ at a current density of 0.1 mA/cm2, stable capacities of ~;;160 mAh/g for y=0 to ~;;110 mAh/g for y=0.2 are achieved. Upon increasing the current density, it is found that all materials containing aluminum show reduced polarization and improved rate performance. The optimal performance at all current densities was found for the compound with y=0.05. The effect of aluminumsubstitution on the crystal structure of the host is discussed

Distinct Surface and Bulk Thermal Behaviors of LiNi0.6Mn0.2Co0.2O2 Cathode Materials as a Function of State of Charge.

Understanding how structural and chemical transformations take place in particles under thermal conditions can inform designing thermally robust electrode materials. Such a study necessitates the use of diagnostic techniques that are capable of probing the transformations at multiple length scales and at different states of charge (SOC). In this study, the thermal behavior of LiNi0.6Mn0.2Co0.2O2 (NMC-622) was examined as a function of SOC, using an array of bulk and surface-sensitive techniques. In general, thermal stability decreases as lithium content is lowered and conversion in the bulk to progressively reduced metal oxides (spinels, rock salt) occurs as the temperature is raised. Hard X-ray absorption spectroscopy (XAS) and X-ray Raman spectroscopy (XRS) experiments, which probe the bulk, reveal that Ni and Co are eventually reduced when partially delithiated samples (regardless of the SOC) are heated, although Mn is not. Surface-sensitive synchrotron techniques, such as soft XAS and transmission X-ray microscopy (TXM), however, reveal that for 50% delithiated samples, apparent oxidation of nickel occurs at particle surfaces under some circumstances. This is partially compensated by reduction of cobalt but may also be a consequence of redistribution of lithium ions upon heating. TXM results indicate the movement of reduced nickel ions into particle interiors or oxidized nickel ions to the surface or both. These experiments illustrate the complexity of the thermal behavior of NMC cathode materials. The study also informs the importance of investigating the surface and bulk difference as a function of SOC when studying the thermal behaviors of battery materials

Comparison of LiMnPO4 made by Combustion and Hydrothermal Syntheses

Among the olivine-structured metal phosphate family, LiMnPO{sub 4} exhibits a high discharge potential (4V), which is still compatible with common electrolytes, making it interesting for use in the next generation of Li ion batteries. The extremely low electronic conductivity of this material severely limits its electrochemical performance, however. One strategy to overcome this limitation is to make LiMnPO{sub 4} nanoparticulate to decrease the diffusion distance. Another is to add a carbon or other conductive coating in intimate contact with the nanoparticles of the main phase, as is commonly done with LiFePO{sub 4}. The electrochemical performance of LiFePO{sub 4} is highly dependent on the quality of the carbon coatings on the particles [1-2], among other variables. Combustion synthesis allows the co-synthesis of nanoparticles coated with carbon in one step. Hydrothermal synthesis is used industrially to make LiFePO{sub 4} cathode materials [3] and affords a good deal of control over purity, crystallinity, and particle size. A wide range of olivine-structured materials has been successfully prepared by this technique [4], including LiMnPO{sub 4} in this study. In this paper, we report on the new synthesis of nano-LiMnPO{sub 4} by a combustion method. The purity is dependent upon the conditions used for synthesis, including the type of fuel and precursors that are chosen. The fuel to nitrate ratio influences the combustion temperature, which determines the type and amount of carbon found in the LiMnPO{sub 4} composites. This can further be modified by use of carbon structural modifiers added during a subsequent (optional) calcination step. Figure 1 shows a transmission electron microscopy (TEM) image of the spherical nano-sized LiMnPO{sub 4} particles typically formed by combustion synthesis. The average particle size is around 30 nm, in agreement with values obtained by the Rietveld refinement of XRD patterns. The small size of the particles cause the peak broadening evident in the pattern of combustion formed LiMnPO{sub 4}, shown in Figure 2. Figure 2 also shows a pattern of hydrothermally prepared LiMnPO{sub 4}, which is sub-micron in size. In this presentation, we will show how the crystallographic parameters, particle size, particle morphology, and carbon content and structure impact the electrochemical properties of the LiMnPO{sub 4}/C composites produced by these methods

Scalable Freeze-Tape-Casting Fabrication and Pore Structure Analysis of 3D LLZO Solid-State Electrolytes.

Nonflammable solid-state electrolytes can potentially address the reliability and energy density limitations of lithium-ion batteries. Garnet-structured oxides such as Li7La3Zr2O12 (LLZO) are some of the most promising candidates for solid-state devices. Here, three-dimensional (3D) solid-state LLZO frameworks with low tortuosity pore channels are proposed as scaffolds, into which active materials and other components can be infiltrated to make composite electrodes for solid-state batteries. To make the scaffolds, we employed aqueous freeze tape casting (FTC), a scalable and environmentally friendly method to produce porous LLZO structures. Using synchrotron radiation hard X-ray microcomputed tomography, we confirmed that LLZO films with porosities of up to 75% were successfully fabricated from slurries with a relatively wide concentration range. The acicular pore size and shape at different depths of scaffolds were quantified by fitting the pore shapes with ellipses, determining the long and short axes and their ratios, and investigating the equivalent diameter distribution. The results show that relatively homogeneous pore sizes and shapes were sustained over a long range along the thickness of the scaffold. Additionally, these pores had low tortuosity and the wall thickness distributions were found to be highly homogeneous. These are desirable characteristics for 3D solid electrolytes for composite electrodes, in terms of both the ease of active material infiltration and also minimization of Li diffusion distances in electrodes. The advantages of the FTC scaffolds are demonstrated by the improved conductivity of LLZO scaffolds infiltrated with poly(ethylene oxide)/lithium bis(trifluoromethanesulfonyl)imide (PEO/LITFSI) compared to those of PEO/LiTFSI films alone or composites containing LLZO particles

Effect of Liquid Electrolyte Soaking on the Interfacial Resistance of Li7La3Zr2O12 for All-Solid-State Lithium Batteries.

The impact of liquid electrolyte soaking on the interfacial resistance between the garnet-structured Li7La3Zr2O12 (LLZO) solid electrolyte and metallic lithium has been studied. Lithium carbonate (Li2CO3) formed by inadvertent exposure of LLZO to ambient conditions is generally known to increase interfacial impedance and decrease lithium wettability. Soaking LLZO powders and pellets in the electrolyte containing lithium tetrafluoroborate (LiBF4) shows a significantly reduced interfacial resistance and improved contact between lithium and LLZO. Raman spectroscopy, X-ray diffraction, and soft X-ray absorption spectroscopy reveal how Li2CO3 is continuously removed with increasing soaking time. On-line mass spectrometry and free energy calculations show how LiBF4 reacts with surface carbonate to form carbon dioxide. Using a very simple and scalable process that does not involve heat-treatment and expensive coating techniques, we show that the Li-LLZO interfacial resistance can be reduced by an order of magnitude