Rate capability of graphite materials as negative electrodes in lithium-ion capacitors

The lithium-ion exchange rate capability of various commercial graphite materials are evaluated using galvanostatic charge/discharge cycling in a half-cell configuration over a wide range of C-rates (0.1 similar to 60C). The results confirm that graphite is capable of de-intercalating stored charge at high rates, but has a poor intercalating rate capability. Decreasing the graphite coating thickness leads to a limited rate performance improvement of the electrode. Reducing the graphite particle size shows enhanced C-rate capability but with increased irreversible capacity loss (ICL). It is demonstrated that the rate of intercalation of lithium-ions into the graphite is significantly limited compared with the corresponding rate of de-intercalation at high C-rates. For the successful utilisation of commercially available conventional graphite as a negative electrode in a lithium-ion capacitor (LIC), its intercalation rate capability needs to be improved or oversized to accommodate high charge rates.

Anionic clay-Pt metal nanoparticle composite through intercalation of hexachloroplatinate in nickel zinc hydroxysalt

Nickel zinc hydroxysalt–Pt metal nanoparticle composite was prepared by intercalation of the anionic platinum complex, [PtCl6]2− in nickel zinc hydroxysalt through ion exchange reaction and subsequent reduction of the platinum complex by ethanol. Powder X-ray diffraction and microscopy studies indicate that the process of reduction of the platinum complex in the interlayer region of the anionic clay takes place topotactically without destroying the layers.

Bismuth sulfide: A high-capacity anode for sodium-ion batteries

Exploring high-performance anode materials is currently one of the most urgent issues towards practical sodium-ion batteries (SIBs). In this work, Bi2S3 is demonstrated to be a high-capacity anode for SIBs for the first time. The specific capacity of Bi2S3 nanorods achieves up to 658 and 264 mAh g-1 at a current density of 100 and 2000 mA g-1, respectively. A full cell with Na3V2(PO4)3-based cathode is also assembled as a proof of concept and delivers 340 mAh g-1 at 100 mA g-1. The sodium storage mechanism of Bi2S3 is investigated by ex-situ XRD coupled with high-resolution TEM (HRTEM), and it is found that sodium storage is achieved by a combined conversion-intercalation mechanism.

Bridging the Ruddlesden–Popper and the Dion–Jacobson series of layered perovskites: synthesis of layered oxides, A2–xLa2Ti3–xNbxO10(A = K, Rb), exhibiting ion exchange

Solid solutions of the formula, A2–xLa2Ti3–xNbxO10(A = K, Rb), exist for the range 0[less-than-or-eq]x[less-than-or-eq]1.0, bridging n= 3 members of the Ruddlesden–Popper series (A2La2Ti3O10) and the Dion–Jacobson series (ALa2Ti2NbO10). For 0[less-than-or-eq]x[less-than-or-eq]0.75, the phases possess body-centred structures characteristic of the Ruddlesden–Popper phases, while the x= 1 members are isostructural with KCa2Nb3O10(A = K) and CsCa2Nb3O10(A = Rb). Protonated derivatives, H2–xLa2Ti3–xNbxO10, which are prepared by ion exchange, retain the structural difference of the parent phases. A difference in the Brønsted acidity of the protonated derivatives revealed by intercalation experiments with organic bases seems to be related to this structural difference.

The intercalation reaction of pyridine with manganese thiophosphate, MnPS3

The intercalation of pyridine in the layered manganese thiophosphate, MnPS3, has been examined in detail by a variety of techniques. The reaction is interesting since none of the anticipated changes in optical and electrical properties associated with intercalation of electron donating molecules is observed. The only notable change in the properties of the host lattice is in the nature of the low-temperature magnetic ordering; while MnPS3 orders antiferromagnetically below 78 K, the intercalated compound shows weak ferromagnetism probably due to a canted spin structure. Vibrational spectra clearly show that the intercalated species are pyridinium ions solvated by neutral pyridine molecules. The corresponding reduced sites of the host lattice, however, were never observed. The molecules in the solvation shell are exchangeable. Although the reaction appears to be topotactic and reversible, from XRD, a more detailed analysis of the products of deintercalation reveal that it is not so. The intercalation proceeds by an ion exchange/intercalation mechanism wherein the intercalated species are pyridinium ions solvated by neutral molecules with charge neutrality being preserved not by electron transfer but by a loss of Mn2+ ions from the lattice. The experimental evidence leading to this conclusion is discussed and it is shown that this model can account satisfactorily for the observed changes (or lack of it) in the optical, electrical, vibrational, and magnetic properties.

The effect of particle size on performance of cathode materials of Li-ion batteries

Beginning with the ‘frog-leg experiment’ by Galvani (1786), followed by the demonstrations of Volta pile by Volta (1792) and lead-acid accumulator by Plante´ (1859), several battery chemistries have been developed and realized commercially. The development of lithium-ion rechargeable battery in the early 1990s is a breakthrough in the science and technology of batteries. Owing to its high energy density and high operating voltage, the Li-ion battery has become the battery of choice for various portable applications such as note-book computers, cellular telephones, camcorders, etc. Huge efforts are underway in succeeding the development of large size batteries for electric vehicle applications. The origin of lithium-ion battery lies in the discovery that Li+-ions can reversibly be intercalated into/de-intercalated from the Van der Walls gap between graphene sheets of carbon materials at a potential close to the Li/Li+ electrode. By employing carbon as the negative electrode material in rechargeable lithium-ion batteries, the problems associated with metallic lithium in rechargeable lithium batteries have been mitigated. Complimentary investigations on intercalation compounds based on transition metals have resulted in establishing LiCoO2 as the promising cathode material. By employing carbon and LiCoO2, respectively, as the negative and positive electrodes in a non-aqueous lithium-salt electrolyte,a Li-ion cell with a voltage value of about 3.5 V has resulted.Subsequent to commercialization of Li-ion batteries, a number of research activities concerning various aspects of the battery components began in several laboratories across the globe. Regarding the positive electrode materials, research priorities have been to develop different kinds of active materials concerning various aspects such as safety, high capacity, low cost, high stability with long cycle-life, environmental compatibility,understanding relationships between crystallographic and electrochemical properties. The present review discusses the published literature on different positive electrode materials of Li-ion batteries, with a focus on the effect of particle size on electrochemical performance.

Nitrates-melt synthesized LiNi0.8Co0.2O2 and its performance as cathode in Li-ion cells

Layered LiNi0.8Co0.2O2 crystallizing in R (3) over barm space group is synthesized by decomposing the constituent metal-nitrate precursors. Oxidizing nature of metal nitrates stabilizes nickel in +3 oxidation state, enabling a high degree of cation ordering in the layered LiNi0.8Co0.2O2. The powder sample characterized by XRD Rietveld refinement reveals <2% Li-Ni site exchange in the layers. Scanning electron microscopic studies on the as-synthesized LiNi0.8Co0.2O2 sample reflect well defined particles of cubic morphology with particle size ranging between 200 and 250 nm. Cyclic voltammograms suggest that LiNi0.8Co0.2O2 undergoes phase transformation on first charge with resultant phase being completely reversible in subsequent cycles. The first-charge-cycle phase transition is further supported by impedance spectroscopy that shows substantial reduction in resistance during initial de-intercalation. Galvanostatic charge-discharge cycles reflect a first-discharge capacity of 184 mAh g(-1) which is stabilized at 170 mAh g(-1) over 50 cycles.

Li3MRuO5 (M = Co, Ni), new lithium-rich layered oxides related to LiCoO2: promising electrochemical performance for possible application as cathode materials in lithium ion batteries

We describe the synthesis and crystal structure of Li3MRuO5 (M = Co and Ni), new rock salt related oxides. Both the oxides crystallize in the layered LiCoO2 (alpha-NaFeO2) structure, as revealed by powder XRD data. Magnetic susceptibility data suggest that the oxidation states of transition metals are Li3Co3+(ls)Ru4+(ls) O-5 (ls = low spin) for the M = Co compound and Li3Ni2+Ru5+O5 for the M = Ni compound. Electrochemical investigations of lithium deintercalation-intercalation behaviour reveal that both Co and Ni phases exhibit attractive specific capacities of ca. 200 mA h g(-1) at an average voltage of 4 V that has been interpreted as due to the oxidation of Co3+ and Ru4+ in Li3CoRuO5 and Ni2+ to Ni4+ in the case of Li3NiRuO5. Thus, a different role of Ru ions is played in the isostructural oxides. Finally, in both cases evidence of irreversible behaviour above 4.2 V is observed and interpreted as formation of high valent ions or alternatively oxidation of oxide ions.

Comparison between granular pillared, organo- and inorgano-organo-bentonites for hydrocarbon and metal ion adsorption

Granular reactive materials have higher permeability and are therefore desirable for in situ groundwater pollution control. Three granular bentonites were prepared: an Al-pillared bentonite (PBg), an organo-bentonite (OBg) using a quaternary ammonium cation (QAC), and an inorgano-organo-bentonite (IOBg), using both the pillaring agent and the QAC. Powdered IOB (IOBp) was also prepared to test the effect of particle size. The modified bentonites were characterised with X-ray diffraction (XRD), Fourier transform infrared spectrometry (FT-IR), thermal gravimetric analysis (TGA) and uniaxial compression tests. The d-spacing increased only with QAC intercalation. The Young's modulus of IOBg was twice as high as OBg. Batch adsorption tests were performed with aqueous multimetal solutions of Pb2+, Cu2+, Cd2+, Zn2+ and Ni2+ ions, with liquid dodecane and with aqueous dodecane solutions. Metal adsorption fit the Langmuir isotherm. Adsorption occurred within 30min for PBg, while the granular organo-bentonite needed at least 12h to reach equilibrium. IOBp had the maximum adsorption capacity at higher metal concentration and lower adsorbent content (Cu2+: 2.2, Ni2+: 1.7, Zn2+: 1.4, Cd2+: 0.9 and Pb2+: 0.7 all in mmolg-1). The dual pillaring of the QAC and Al hydroxide increased the adsorption. The adsorption of liquid dodecane was in the order IOBg>OBg>PBg (3.2>2.7>1.7mmolg-1). Therefore IOBg has potential for the removal of toxic compounds found in soil, groundwater, storm water and wastewater. © 2012 Elsevier B.V.

A study of cokes used as anodic materials in lithium ion rechargeable batteries

A variety of cokes pretreated at different temperatures are used as anodic materials and their electrochemical characteristics are examined by cyclic voltammetry. It is found that for some cokes such as petroleum coke (preheated at 1300 degrees C), pitch coke (1300 degrees C), needle coke (1900 degrees C), metallurgical coke (1900 degrees C), high capacity and cyclic efficiency are achieved. Needle coke (1900 degrees C) and metallurgical coke (1900 degrees C) in particular give a capacity of over 200 mAh/g and a cyclic efficiency of nearly 100%, whereas poor performance is exhibited by those pretreated at higher or lower temperatures, e.g., petroleum cokes (500 degrees C, 2800 degrees C), pitch coke (500 degrees C) and needle coke (2800 degrees C). The cyclic voltammograms show two electrochemical processes, one at about 0.1 V vs. Li+/Li which is electrochemically reversible, and may be attributed to the intercalation/deintercalation of lithium ions while the other, at about 0.6 V vs. Li+/Li, is electrochemically irreversible and may be assigned to the decomposition of the electrolyte solvent, which leads to formation of the passive film on the anode surface. The experimental results strongly suggest that the pretreatment temperature of cokes and of the solvent are determining factors for the growth, structure and properties of the passive film.

Nanostructured materials for Lithium-ion battery technology

The Li-ion battery has for several years been at the forefront of powering an ever-increasing number of modem consumer electronic devices such as laptops, tablet PCs, cell phones, portable music players etc., while in more recent times, has also been sought to power a range of emerging electric and hybrid-electric vehicle classes. Given their extreme popularity, a number of features which define the performance of the Li-ion battery have become a target of improvement and have garnered tremendous research effort over the past two decades. Features such as battery capacity, voltage, lifetime, rate performance, together with important implications such as safety, environmental benignity and cost have all attracted attention. Although properties such as cell voltage and theoretical capacity are bound by the selection of electrode materials which constitute its interior, other performance makers of the Li-ion battery such as actual capacity, lifetime and rate performance may be improved by tailoring such materials with characteristics favourable to Li+ intercalation. One such tailoring route involves shrinking of the constituent electrode materials to that of the nanoscale, where the ultra-small diameters may bestow favourable Li+ intercalation properties while providing a necessary mechanical robustness during routine electrochemical operation. The work detailed in this thesis describes a range of synthetic routes taken in nanostructuring a selection of choice Li-ion positive electrode candidates, together with a review of their respective Li-ion performances. Chapter one of this thesis serves to highlight a number of key advancements which have been made and detailed in the literature over recent years pertaining to the use of nanostructured materials in Li-ion technology. Chapter two provides an overview of the experimental conditions and techniques employed in the synthesis and electrochemical characterisation of the as-prepared electrode materials constituting this doctoral thesis. Chapter three details the synthesis of small-diameter V2O5 and V2O5/TiO2 nanocomposite structures prepared by a novel carbon nanocage templating method using liquid precursors. Chapter four details a hydrothermal synthesis and characterisation of nanostructured β-LiVOPO4 powders together with an overview of their Li+ insertion properties while chapter five focuses on supercritical fluid synthesis as one technique in the tailoring of FeF2 and CoF2 powders having potentially appealing Li-ion 'conversion' properties. Finally, chapter six summarises the overall conclusions drawn from the results presented in this thesis, coupled with an indication of potential future work which may be explored upon the materials described in this work.

Fabrication and characterization of doped and porous silicon nanowires as anodes for lithium ion batteries

By using Si(100) with different dopant type (n++-type (As) or p-type (B)), it is shown how metal-assisted chemically (MAC) etched silicon nanowires (Si NWs) can form with rough outer surfaces around a solid NW core for p-type NWs, and a unique, defined mesoporous structure for highly doped n-type NWs. High resolution electron microscopy techniques were used to define the characteristic roughening and mesoporous structure within the NWs and how such structures can form due to a judicious choice of carrier concentration and dopant type. Control of roughness and internal mesoporosity is demonstrated during the formation of Si NWs from highly doped n-type Si(100) during electroless etching through a systematic investigation of etching parameters (etching time, AgNO3 concentration, %HF and temperature). Raman scattering measurements of the transverse optical phonon confirm quantum size effects and phonon scattering in mesoporous wires associated with the etching condition, including quantum confinement effects for the nanocrystallites of Si comprising the internal structure of the mesoporous NWs. Laser power heating of NWs confirms phonon confinement and scattering from internal mesoporosity causing reduced thermal conductivity. The Li+ insertion and extraction characteristics at n-type and p-type Si(100) electrodes with different carrier density and doping type are investigated by cyclic voltammetry and constant current measurements. The insertion and extraction potentials are demonstrated to vary with cycling and the occurrence of an activation effect is shown in n-type electrodes where the charge capacity and voltammetric currents are found to be much higher than p-type electrodes. X-ray photo-electron spectroscopy (XPS) and Raman scattering demonstrate that highly doped n-type Si(100) retains Li as a silicide and converts to an amorphous phase as a two-step phase conversion process. The findings show the succinct dependence of Li insertion and extraction processes for uniformly doped Si(100) single crystals and how the doping type and its effect on the semiconductor-solution interface dominate Li insertion and extraction, composition, crystallinity changes and charge capacity. The effect of dopant, doping density and porosity of MAC etched Si NWs are investigated. The CV response is shown to change in area (current density) with increasing NW length and in profile shape with a changing porosity of the Si NWs. The CV response also changes with scan rate indicative of a transition from intercalation or alloying reactions, to pseudocapactive charge storage at higher scan rates and for p-type NWs. SEM and TEM show a change in structure of the NWs after Li insertion and extraction due to expansion and contraction of the Si NWs. Galvanostatic measurements show the cycling behavior and the Coulombic efficiency of the Si NWs in comparison to their bulk counterparts.

Lithium Ion Electro-Insertion and Spectroelectrochemical Properties of Films from Hexaniobate

Layer-by-layer (LbL) films from K(2)Nb(6)O(17)(2-) and polyallylamine (PAH) and dip-coating films of H(2)K(2)Nb(6)O(17) were prepared on a fluorine-doped tin-oxide (FTO)-coated glass. The atomic force microscopy (AFM) images were carried out for morphological characterization of both materials. The real surface area and the roughness factor were determined on the basis of pseudocapacitive processes involved in the electroreduction/electrooxidation of gold layers deposited on these films. Next, lithium ion insertion into these materials was examined by means of electrochemical and spectroelectrochemical measurements. More specifically, cyclic voltammetry and current pulses under visible light beams were used to investigate mass transport and chromogenic properties. The lithium ion diffusion coefficient (D(Li)) within the LbL matrix is significantly higher than that within the dip-coating film, ensuring high storage capacity of lithium ions in the self-assembled electrode. Contrary to the LbL film, the potentiodynamic profile of absorbance change (Delta A) as a function of time is not similar to that obtained in the case of current density for the dip-coating film. Aiming at analyzing the rate of the coloration front associated with lithium ion diffusion, a spectroelectrochemical method based on the galvanostatic intermittent titration technique (GITT) was employed so as to determine the ""optical"" diffusion coefficient (D(op)). In the dip-coating film, the method employed here revealed that the lithium ion rate is higher in diffusion pathways formed from K(2)Nb(6)O(17)(2-) sites that contribute more significantly to Delta A. Meanwhile, the presence of PAH contributed to the increased ionic mobility in diffusion pathways in the LbL film, with low contribution to the electrochromic efficiency. These results aided a better understanding of the potentiodynamic profile of the temporal change of absorbance and current density during the insertion/deinsertion of lithium ions into the electrochromic materials.

Thermodynamics and Lithium Intercalation in CeO(2)-TiO(2) Thin Film

The kinetics and the thermodynamics of electrochemical intercalation of lithium into CeO(2)-TiO(2) films prepared by the sol-gel process were studied by galvanostatic intermittent titration technique (GITT) as function of the depth of lithium intercalation. The open-circuit-potential versus x in Li(x)(CeO(2)-TiO(2)) curve consists of two straight lines with different slopes, one in the range of 0.03 <= x <= 0.09 and the other of 0.09 < x <= 0.15. The standard Gibbs energy for lithium intercalation Delta G(1)(0) was 6kJ/mol for x = 0.09 in Li(x)(CeO(2)-TiO(2)) at room temperature. The chemical diffusion coefficient value, D(Li+), of lithium intercalation into thin film oxide was 2.14.10(-11) cm(2)/s at x = 0.15, and the value of the component diffusion coefficient D(Li+),(k) was about one order of magnitude lower than the coefficient of chemical diffusion.

Kinetic aspects of ion exchange in KhFek[Fe(CN)(6)](l)center dot mH(2)O compounds: A combined electrical and mass transfer functions approach

The present paper quantifies and develops the kinetic aspects involved in the mechanism of interplay between electron and ions presented elsewhere(1) for KhFek[Fe(CN)(6)](l)center dot mH(2)O (Prussian Blue) host materials. Accordingly, there are three different electrochemical processes involved in the PB host materials: H3O+, K+, and H+ insertion/extraction mechanisms which here were fully kinetically studied by means of the use of combined electronic and mass transfer functions as a tool to separate all the processes. The use of combined electronic and mass transfer functions was very important to validate and confirm the proposed mechanism. This mechanism allows the electrochemical and chemical processes involved in the KhFek[Fe(CN)(6)](l)center dot mH(2)O host and Prussian Blue derivatives to be understood. In addition, a formalism was also developed to consider superficial oxygen reduction. From the analysis of the kinetic processes involved in the model, it was possible to demonstrate that the processes associated with K+ and H+ exchanges are reversible whereas the H3O+ insertion process was shown not to present a reversible pattern. This irreversible pattern is very peculiar and was shown to be related to the catalytic proton reduction reaction. Furthermore, from the model, it was possible to calculate the number density of available sites for each intercalation/deintercalation processes and infer that they are very similar for K+ and H+. Hence, the high prominence of the K+ exchange observed in the voltammetric responses has a kinetic origin and is not related to the amount of sites available for intercalation/deintercalation of the ions.