Studies on 12 V substrate-integrated lead-carbon hybrid ultracapacitors

A cost-effective 12 V substrate-integrated lead-carbon hybrid ultracapacitor is developed and performance tested. These hybrid ultracapacitors employ flexible-graphite sheets as negative plate current-collectors that are coated amperometrically with a thin layer of conducting polymer, namely poly-aniline to provide good adhesivity to activated-carbon layer. The positive plate of the hybrid ultracapacitors comprise conventional lead-sheet that is converted electrochemically into a substrate-integrated lead-dioxide electrode. 12 V substrate-integrated lead-carbon hybrid ultracapacitors both in absorbent-glass-mat and polymeric silica-gel electrolyte configurations are fabricated and characterized. It is possible to realize 12 V configurations with capacitance values of similar to 200 F and similar to 300 F, energy densities of similar to 1.9 Wh kg(-1) and similar to 2.5 Wh kg(-1) and power densities of similar to 2 kW kg(-1) and similar to 0.8 kW kg(-1), respectively, having faradaic-efficiency values of similar to 90 % with cycle-life in excess of 100,000 cycles. The effective cost of the mentioned hybrid ultracapacitors is estimated to be about similar to 4 US$/Wh as compared to similar to 20 US$/Wh for commercially available ultracapacitors.

Na2.44Mn1.79(SO4)(3): a new member of the alluaudite family of insertion compounds for sodium ion batteries

Sodium-ion batteries have been extensively pursued as economic alternatives to lithium-ion batteries. Investigating the polyanion chemistry, alluaudite structured Na2Fe2II(SO4)(3) has been recently discovered as a 3.8 V positive electrode material (Barpanda et al., Nature Commun., 5: 4358, 2014). Registering the highest ever Fe-III/Fe-II redox potential (vs. Na/Na+) and formidable energy density, it has opened up a new polyanion family for sodium batteries. Exploring the alluaudite family, here we report isotypical Na2+2xMn2-xII(SO4)(3) (x = 0.22) as a novel high-voltage cathode material for the first time. Following low-temperature (ca. 350 degrees C) solid-state synthesis, the structure of this new alluaudite compound has been solved adopting a monoclinic framework (s.g. C2/c) showing antiferromagnetic ordering at 3.4 K. Synergising experimental and ab initio DFT investigation, Na2+2xMn2-xII(SO4)(3) has been found to be a potential high-voltage (ca. 4.4 V) cathode material for sodium batteries.

Ultra-small sulphur nanoparticles configured inside a flexible organic mixed conducting network as a cathode for lithium-sulphur batteries

The major challenges in Li-S batteries are the formation of soluble polysulphides during the reversible conversion of S-8 <-> Li2S, large changes in sulphur particle volume during lithiation and extremely poor charge transport in sulphur. We demonstrate here a novel and simple strategy to overcome these challenges towards practical realization of a stable high performance Li-S battery. For the first time, a strategy is developed which does away with the necessity of pre-fabricated high surface area hollow-structured adsorbates and also multiple nontrivial synthesis steps related to sulphur loading inside such adsorbates. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li-S batteries. The PEG and PAni network around the sulphur nanoparticles serves as an efficient flexible trap for sulphur and polysulphides and also provides distinct pathways for electrons (through PAni) and ions (through PEG) during battery operation. Contrary to the cathodes demonstrated based on various carbon-sulphur composites, the mixed conducting S-MIEC showed an extremely high loading of 75%. The S-MIEC exhibited a stable capacity of nearly 900 mA h g(-1) at the end of 100 cycles at a 1C current rate.

A Fast-Locking Phase-Locked Loop Using a Seven-State Phase Frequency Detector

A seven-state phase frequency detector (S.S PFD) is proposed for fast-locking charge pump based phase-locked loops (CPPLLs) in this paper. The locking time of the PLL can be significantly reduced by using the seven-state PFD to inject more current into the loop filter. In this stage, the bandwidth of the PLL is increased or decreased to track the phase difference of the reference signal and the feedback signal. The proposed architecture is realized in a standard 0.35 mu m 2P4M CMOS process with a 3.3V supply voltage. The locking time of the proposed PLL is 1.102 mu s compared with the 2.347 mu s of the PLL based on continuous-time PFD and the 3.298 mu s of the PLL based on the pass-transistor tri-state PFD. There are 53.05% and 66.59% reductions of the locking time. The simulation results and the comparison with other PLLs demonstrate that the proposed seven-state PFD is effective to reduce locking time.

Simulation of a monolithically integrated CMOS bioamplifier for EEG recordings

A monolithically integrated CMOS bioamplifier is presented in this paper for EEG recording applications. The capacitive-coupled circuit input structure is utilized to eliminate the large and random DC offsets existing in the electrode-tissue interface. Diode-connected NMOS transistors with negative voltage between gate and source are candidates for large resistors necessary to the bioamplifier. A passive BEF (Band Eliminator Filter) can reduce 50 Hz noise disturbance strength by more than 60 dB. A novel analysis approach is given to help determine the noise power spectral density. Simulation results show that the two-stage CMOS bioamplifier in a closed-loop capacitive feedback configuration,provides an AC in-band gain of 39.6 dB, a DC gain of zero, and an input-referred noise of 87 nVrms integrated from 0.01 Hz to 100 Hz.

Improvement of CMOS SOS devices characteristics by a modified solid phase epitaxy

CMOS/SOS devices have lower carriers mobility and higher channel leakage current than bulk silicon CMOS devices. These mainly results from the defects of heteroepitaxial silicon film, especially from the defects near Si-Sapphire interface. This paper describes the experiment results of CMOS/SOS devices characteristics improved by a better epitaxial silicon quality which is obtained by a modified solid phase epitaxy.

The structure and electrochemical characteristics of La0.67Mg0.33 (Ni0.8Co0.1Mn0.1)(x) (x=2.5-5.0) multiphase alloys for nickel-metal hydride batteries

This paper presents results concerning structure and electrochemical characteristics of the La0.67Mg0.33 (Ni0.8Co0.1Mn0.1) (x) (x=2.5-5.0) alloy. It can be found from the result of the Rietveld analyses that the structures of the alloys change obviously with increasing x from 2.5 to 5.0. The main phase of the alloys with x=2.5-3.5 is LaMg2Ni9 phase with a PuNi3-type rhombohedral structure, but the main phase of the alloys with x=4.0-5.0 is LaNi(5)phase with a CaCu5-type hexagonal structure. Furthermore, the phase ratio, lattice parameter and cell volume of the LaMg2Ni9 phase and the LaNi5 phase change with increasing x. The electrochemical studies show that the maximum discharge capacity increases from 214.7 mAh/g (x=2.5) to 391.1 mAh/g (x=3.5) and then decreases to 238.5 mAh/g (x=5.0). As the discharge current density is 1,200 mA/g, the high rate dischargeability (HRD) increases from 51.1% (x=2.5) to 83.7% (x=3.5) and then decreases to 71.6% (x=5.0). Moreover, the exchange current density (I-0) of the alloy electrodes first increases and then decrease with increasing x from 2.5 to 5.0, which is consistent with the variation of the HRD. The cell volume reduces with increasing x in the alloys, which is detrimental to hydrogen diffusion and accordingly decreases the low-temperature dischargeability of the alloy electrodes.

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.

A detailed study of the lithiation of iron phosphate as well as the development of a novel synthesis of lithium iron silicate as cathode material for lithium-ion batteries

Dans cette thèse nous démontrons le travail fait sur deux matériaux de cathodes pour les piles lithium-ion. Dans la première partie, nous avons préparé du phosphate de fer lithié (LiFePO4) par deux méthodes de lithiation présentées dans la littérature qui utilisent du phosphate de fer (FePO4) amorphe comme précurseur. Pour les deux méthodes, le produit obtenu à chaque étape de la synthèse a été analysé par la spectroscopie Mössbauer ainsi que par diffraction des rayons X (DRX) pour mieux comprendre le mécanisme de la réaction. Les résultats de ces analyses ont été publiés dans Journal of Power Sources. Le deuxième matériau de cathode qui a été étudié est le silicate de fer lithié (Li2FeSiO4). Une nouvelle méthode de synthèse a été développée pour obtenir le silicate de fer lithié en utilisant des produits chimiques peu couteux ainsi que de l’équipement de laboratoire de base. Le matériau a été obtenu par une synthèse à l’état solide. Les performances électrochimiques ont été obtenues après une étape de broyage et un dépôt d’une couche de carbone. Un essai a été fait pour synthétiser une version substituée du silicate de fer lithié dans le but d’augmenter les performances électrochimiques de ce matériau.

Low cost synthesis of cathode and anode materials for lithium-ion batteries

Dans cette thèse, nous démontrons des travaux sur la synthèse à faible coût des matériaux de cathode et l'anode pour les piles lithium-ion. Pour les cathodes, nous avons utilisé des précurseurs à faible coût pour préparer LiFePO4 et LiFe0.3Mn0.7PO4 en utilisant une méthode hydrothermale. Tout d'abord, des matériaux composites (LiFePO4/C) ont été synthétisés à partir d'un précurseur de Fe2O3 par une procédé hydrothermique pour faire LiFePO4(OH) dans une première étape suivie d'une calcination rapide pour le revêtement de carbone. Deuxièmement, LiFePO4 avec une bonne cristallinité et une grande pureté a été synthétisé en une seule étape, avec Fe2O3 par voie hydrothermale. Troisièmement, LiFe0.3Mn0.7PO4 a été préparé en utilisant Fe2O3 et MnO comme des précurseurs de bas coûts au sein d'une méthode hydrothermale synthétique. Pour les matériaux d'anode, nous avons nos efforts concentré sur un matériau d'anode à faible coût α-Fe2O3 avec deux types de synthèse hydrothermales, une a base de micro-ondes (MAH) l’autre plus conventionnelles (CH). La nouveauté de cette thèse est que pour la première fois le LiFePO4 a été préparé par une méthode hydrothermale en utilisant un précurseur Fe3+ (Fe2O3). Le Fe2O3 est un précurseur à faible coût et en combinant ses coûts avec les conditions de synthèse à basse température nous avons réalisé une réduction considérable des coûts de production pour le LiFePO4, menant ainsi à une meilleure commercialisation du LiFePO4 comme matériaux de cathode dans les piles lithium-ion. Par cette méthode de préparation, le LiFePO4/C procure une capacité de décharge et une stabilité de cycle accrue par rapport une synthétisation par la méthode à l'état solide pour les mêmes précurseurs Les résultats sont résumés dans deux articles qui ont été récemment soumis dans des revues scientifiques.

Growth of V2O5 nanorods from ball-milled powders and their performance in cathodes and anodes of lithium-ion batteries

The two-stage procedure of ball milling and annealing in air represents a prospective method of preparing nanorods of V₂O₅ with electrochemical properties suitable for the application in lithium-ion batteries. Commercially purchased V₂O₅ powder is milled in a ball mill as the first step of the synthesis. The as-milled precursor is subsequently annealed in air to produce the morphology of nanorods via solid-state recrystallization. We have recently investigated intermediate stages of the formation of nanorods, and this paper summarizes the synthesis method including the description of the current understanding of the growth mechanism. The obtained V₂O₅ nanorods have been assessed as an electrode material for both anodes and cathodes of lithium-ion batteries. When used in cathodes, the nanorods demonstrate a better retention of capacity upon cycling than that of the commercially available powder of V₂O₅. When used in anodes, the performances of nanorods and the reference V₂O₅ powder are similar to a large extent, which is related to a different operating mechanism of V₂O₅ in anodes. The experimentally observed capacity of V₂O₅ nanorods in an anode has stabilized at the level of about 450 mAh/g after few cycles.

An organic ionic plastic crystal electrolyte for rate capability and stability of ambient temperature lithium batteries

Reliable, safe and high performance solid electrolytes are a critical step in the advancement of high energy density secondary batteries. In the present work we demonstrate a novel solid electrolyte based on the organic ionic plastic crystal (OIPC) triisobutyl(methyl)phosphonium bis(fluorosulfonyl)imide (P1444FSI). With the addition of 4 mol% LiFSI, the OIPC shows a high conductivity of 0.26 mS cm-1 at 22 °C. The ion transport mechanisms have been rationalized by compiling thermal phase behaviour and crystal structure information obtained by variable temperature synchrotron X-ray diffraction. With a large electrochemical window (ca. 6 V) and importantly, the formation of a stable and highly conductive solid electrolyte interphase (SEI), we were able to cycle lithium cells (LiLiFePO4) at 30 °C and 20 °C at rates of up to 1 C with good capacity retention. At the 0.1 C rate, about 160 mA h g-1 discharge capacity was achieved at 20 °C, which is the highest for OIPC based cells to date. It is anticipated that these small phosphonium cation and [FSI] anion based OIPCs will show increasing significance in the field of solid electrolytes.