Robert Dominko

Impact of the Carbon Coating Thickness on the Electrochemical Performance of LiFePO4 / C Composites

Porous, well crystalline LiFePO 4 /C composites with different amounts of carbon have been prepared by a sol-gel technique. The thickness of carbon coatings (paintings) has been determined by high-resolution transmission electron microscopy. It is shown that carbon coating thickness can be controlled by the amount of carbon and it has an impact on the obtained reversible capacity. Furthermore, it is shown that atomic ratio of nonactive Fe(III) phase (presumably Fe 3 P) in as-synthesized LiFePO 4 /C composites depends on the amount of carbon in the composite. Using Mossbauer spectroscopy, we have confirmed that the nonactive Fe(III) remains nearly unchanged in the composite during cycling. The lowest amount of carbon in LiFePO 4 /C composites obtained from citrate anion as a gelling agent was 3.2 wt % and this particular amount corresponds to the carbon coating thickness of about 1-2 nm. The reversible capacity obtained from the above-mentioned composite delivers close to 80% of the theoretical capacity at room temperature with a current density of 170 mA/g (C/1 rate).

Cathode composites for Li-S batteries via the use of oxygenated porous architectures.

Li-S rechargeable batteries are attractive for electric transportation because of their low cost, environmentally friendliness, and superior energy density. However, the Li-S system has yet to conquer the marketplace, owing to its drawbacks, namely, soluble polysulfide formation. To tackle this issue, we present here a strategy based on the use of a mesoporous chromium trimesate metal-organic framework (MOF) named MIL-100(Cr) as host material for sulfur impregnation. Electrodes containing sulfur impregnated within the pores of the MOF were found to show a marked increase in the capacity retention of Li-S cathodes. Complementary transmission electron microscopy and X-ray photoelectron spectroscopy measurements demonstrated the reversible capture and release of the polysulfides by the pores of MOF during cycling and evidenced a weak binding between the polysulphides and the oxygenated framework. Such an approach was generalized to other mesoporous oxide structures, such as mesoporous silica, for instance SBA-15, having the same positive effect as the MOF on the capacity retention of Li-S cells. Besides pore sizes, the surface activity of the mesoporous additives, as observed for the MOF, appears to also have a pronounced effect on enhancing the cycle performance. Increased knowledge about the interface between polysulfide species and oxide surfaces could lead to novel approaches in the design and fabrication of long cycle life S electrodes.

Silicate cathodes for lithium batteries: alternatives to phosphates?

Polyoxyanion compounds, particularly the olivine-phosphate LiFePO4, are receiving considerable attention as alternative cathodes for rechargeable lithium batteries. More recently, an entirely new class of polyoxyanion cathodes based on the orthosilicates, Li2MSiO4 (where M = Mn, Fe, and Co), has been attracting growing interest. In the case of Li2FeSiO4, iron and silicon are among the most abundant and lowest cost elements, and hence offer the tantalising prospect of preparing cheap and safe cathodes from rust and sand! This Highlight presents an overview of recent developments and future challenges of silicate cathode materials focusing on their structural polymorphs, electrochemical behaviour and nanomaterials chemistry.

The role of carbon black distribution in cathodes for Li ion batteries

Abstract The influence of carbon black distribution/arrangement in cathode composite on cathode performance is studied using three types of active materials: LiMn2O2-spinel, LiCoO2, and LiFePO4. To the active materials, carbon black is added in two different ways: (a) using a conventional mixing procedure and (b) using a novel coating technology (NCT) invented in our laboratory. Different technologies yield different arrangement (distribution) of carbon black around active particles. It is shown that the uniformity of carbon black distribution affects significantly the cathode kinetics, regardless of the type of active particles used. A simple model explaining the influence of carbon black distribution on cathode kinetics is presented.

The Importance of Interphase Contacts in Li Ion Electrodes : The Meaning of the High-Frequency Impedance Arc

Li insertion electrodes are made by pressing a mixture of active material and additives on a metallic substrate. Here we estimate how various interphase contacts affect the electrode kinetics. We apply variable external mechanical pressure onto different cathodes and measure their impedance response. Similar experiments are performed on dry composites in contact with: Al or Cu foil, or Ag paste. Most surprisingly, we find that the high-frequency impedance arc is due to the contact impedance between the metal and the electrode material. This is in fundamental contradiction with previous interpretations. We propose an equivalent circuit explaining the observed phenomena.

Dependence of Li2FeSiO4 Electrochemistry on Structure

Small differences in the FeO(4) arrangements (orientation, size, and distortion) do influence the equilibrium potential measured during the first oxidation of Fe(2+) to Fe(3+) in all polymorphs of Li(2)FeSiO(4).

Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries

Peering into cathode layered oxides The quest for better rechargeable batteries means finding ways to pack more energy into a smaller mass or volume. Lithium layered oxides are a promising class of materials that could double storage capacities. However, the design of safe and long-lasting batteries requires an understanding of the physical and chemical changes that occur during redox processes. McCalla et al. used a combination of experiments and calculations to understand the formation of O-O dimers, which are key to improving the properties of these cathode materials. Science, this issue p. 1516 A model lithium layered oxide is used to probe the enhanced charge storage capacity of this family of materials. Lithium-ion (Li-ion) batteries that rely on cationic redox reactions are the primary energy source for portable electronics. One pathway toward greater energy density is through the use of Li-rich layered oxides. The capacity of this class of materials (>270 milliampere hours per gram) has been shown to be nested in anionic redox reactions, which are thought to form peroxo-like species. However, the oxygen-oxygen (O-O) bonding pattern has not been observed in previous studies, nor has there been a satisfactory explanation for the irreversible changes that occur during first delithiation. By using Li2IrO3 as a model compound, we visualize the O-O dimers via transmission electron microscopy and neutron diffraction. Our findings establish the fundamental relation between the anionic redox process and the evolution of the O-O bonding in layered oxides.

Impact of LiFePO4 ∕ C Composites Porosity on Their Electrochemical Performance

Fe(III) citrate was used as a source for synthesis of microsized porous LiFePO 4 /C particles. All samples, prepared either by solid-state or by sol-gel techniques, are phase-pure triphylite phases, which, however, have different morphology highly influenced by the type of synthesis and synthesis parameters. Their common feature is porosity due to thermal decomposition of citrate anion. The impact of particle porosity on the electrochemical behavior is discussed in terms of qualitative results obtained from scanning electron microscopy (SEM) micrographs and in terms of quantitative results obtained from N 2 adsorption isotherms. The best electrochemical behavior (above 140 mAh/g at C/2 rate during continuous cycling) was obtained with composites prepared at a relatively high heating rate (above 5 K/min). This suggests that interlaced pores were formed inside particles. A strong correlation between the electrochemical results and the heating rate was observed, which could easily be explained based on SEM micrographs and on some trends found in porosity measurements. The latter reveal the main difference between samples prepared by solid-state and by sol-gel techniques.

Influence of carbon black distribution on performance of oxide cathodes for Li ion batteries

Abstract The influence of carbon black content and carbon black distribution on performance of oxide-based cathodes, such as LiCoO 2 and LiMn 2 O 4 , is investigated. The electronic conductivity of oxide material/carbon black composites is compared with electrochemical characteristics of the same composites. Uniformity of carbon black distribution in cathode composites is achieved using novel coating technology in cathode preparation. In this technology, the active particles are first pretreated in a gelatin solution. The adsorbed gelatin then controls the deposition of carbon black so that carbon black particles are uniformly distributed in the final composite. The influence of various parameters, such as pH of gelatin, amount of gelatin and concentration of carbon black on the uniformity of carbon black distribution is investigated. It is shown that the conventional technology of cathode preparation yields quite non-uniform distribution of carbon black in cathode material. At the end, we demonstrate that uniformity of carbon black distribution has a crucial impact on reversible capacity, especially at high current densities.

Cellulose as a binding material in graphitic anodes for Li ion batteries: a performance and degradation study

Four types of cellulose, in particular carboxy methyl cellulose (CMC), are tested as potential binding materials in graphitic anodes for lithium ion batteries. It is shown that a minimum content of a cellulose which gives acceptable anode properties (reversible capacity>300 mA h g−1 during the first 10 cycles, irreversible loss<20%) is about 2 wt.%, which is less than in the case of conventional polymeric binders (5–10 wt.%). Kinetics of insertion–deinsertion and passivation processes seem not to be affected by the presence of cellulose. Explanation for the electrode failure at cellulose contents lower than 1 wt.% is given based on X-ray diffraction and microscopy investigations. Finally, the structure (distribution) of cellulose in the composite anode material is discussed and (indirectly) checked with a series of experiments. Most results are compared with the corresponding results obtained either with gelatin or conventional polymeric binders or both.