Phenothiazine based polymers for energy and data storage application

Die vorliegende Arbeit befasst sich mit der Synthese und Charakterisierung von Polymeren mit redox-funktionalen Phenothiazin-Seitenketten. Phenothiazin und seine Derivate sind kleine Redoxeinheiten, deren reversibles Redoxverhalten mit electrochromen Eigenschaften verbunden ist. Das besondere an Phenothiazine ist die Bildung von stabilen Radikalkationen im oxidierten Zustand. Daher können Phenothiazine als bistabile Moleküle agieren und zwischen zwei stabilen Redoxzuständen wechseln. Dieser Schaltprozess geht gleichzeitig mit einer Farbveränderung an her.rnrnIm Rahmen dieser Arbeit wird die Synthese neuartiger Phenothiazin-Polymere mittels radikalischer Polymerisation beschrieben. Phenothiazin-Derivate wurden kovalent an aliphatischen und aromatischen Polymerketten gebunden. Dies erfolgte über zwei unterschiedlichen synthetischen Routen. Die erste Route beinhaltet den Einsatz von Vinyl-Monomeren mit Phenothiazin Funktionalität zur direkten Polymerisation. Die zweite Route verwendet Amin modifizierte Phenothiazin-Derivate zur Funktionalisierung von Polymeren mit Aktivester-Seitenketten in einer polymeranalogen Reaktion. rnrnPolymere mit redox-funktionalen Phenothiazin-Seitenketten sind aufgrund ihrer Elektron-Donor-Eigenschaften geeignete Kandidaten für die Verwendung als Kathodenmaterialien. Zur Überprüfung ihrer Eignung wurden Phenothiazin-Polymere als Elektrodenmaterialien in Lithium-Batteriezellen eingesetzt. Die verwendeten Polymere wiesen gute Kapazitätswerte von circa 50-90 Ah/kg sowie schnelle Aufladezeiten in der Batteriezelle auf. Besonders die Aufladezeiten sind 5-10 mal höher als konventionelle Lithium-Batterien. Im Hinblick auf Anzahl der Lade- und Entladezyklen, erzielten die Polymere gute Werte in den Langzeit-Stabilitätstests. Insgesamt überstehen die Polymere 500 Ladezyklen mit geringen Veränderungen der Anfangswerte bezüglich Ladezeiten und -kapazitäten. Die Langzeit-Stabilität hängt unmittelbar mit der Radikalstabilität zusammen. Eine Stabilisierung der Radikalkationen gelang durch die Verlängerung der Seitenkette am Stickstoffatom des Phenothiazins und der Polymerhauptkette. Eine derartige Alkyl-Substitution erhöht die Radikalstabilität durch verstärkte Wechselwirkung mit dem aromatischen Ring und verbessert somit die Batterieleistung hinsichtlich der Stabilität gegenüber Lade- und Entladezyklen. rnrnDes Weiteren wurde die praktische Anwendung von bistabilen Phenothiazin-Polymeren als Speichermedium für hohe Datendichten untersucht. Dazu wurden dünne Filme des Polymers auf leitfähigen Substraten elektrochemisch oxidiert. Die elektrochemische Oxidation erfolgte mittels Rasterkraftmikroskopie in Kombination mit leitfähigen Mikroskopspitzen. Mittels dieser Technik gelang es, die Oberfläche des Polymers im nanoskaligen Bereich zu oxidieren und somit die lokale Leitfähigkeit zu verändern. Damit konnten unterschiedlich große Muster lithographisch beschrieben und aufgrund der Veränderung ihrer Leitfähigkeit detektiert werden. Der Schreibprozess führte nur zu einer Veränderung der lokalen Leitfähigkeit ohne die topographische Beschaffenheit des Polymerfilms zu beeinflussen. Außerdem erwiesen sich die Muster als besonders stabil sowohl mechanisch als auch über die Zeit.rnrnZum Schluss wurden neue Synthesestrategien entwickelt um mechanisch stabile als auch redox-funktionale Oberflächen zu produzieren. Mit Hilfe der oberflächen-initiierten Atomtransfer-Radikalpolymerisation wurden gepfropfte Polymerbürsten mit redox-funktionalen Phenothiazin-Seitenketten hergestellt und mittels Röntgenmethoden und Rasterkraftmikroskopie analysiert. Eine der Synthesestrategien geht von gepfropften Aktivesterbürsten aus, die anschließend in einem nachfolgenden Schritt mit redox-funktionalen Gruppen modifiziert werden können. Diese Vorgehensweise ist besonders vielversprechend und erlaubt es unterschiedliche funktionelle Gruppen an den Aktivesterbürsten zu verankern. Damit können durch Verwendung von vernetzenden Gruppen neben den Redoxeigenschaften, die mechanische Stabilität solcher Polymerfilme optimiert werden. rn rn

Electrodes for Long-Term Esophageal Electrocardiography

The emerging application of long-term and high-quality ECG recording requires alternative electrodes to improve the signal quality and recording capability of surface skin electrodes. The esophageal ECG has the potential to overcome these limitations but necessitates novel recorder and lead designs. The electrode material is of particular interest, since the material has to ensure conflicting requirements like excellent biopotential recording properties and inertness. To this end, novel electrode materials like PEDOT and silver-PDMS as well as established electrode materials such as stainless steel, platinum, gold, iridium oxide, titanium nitride, and glassy carbon were investigated by long-term electrochemical impedance spectroscopy and model-based signal analysis using the derived in vitro interfacial properties in conjunction with a dedicated ECG amplifier. The results of this novel approach show that titanium nitride and iridium oxide featuring microstructured surfaces did not degrade when exposed to artificial acidic saliva. These materials provide low electrode potential drifts and insignificant signal distortion superior to surface skin electrodes making them compatible with accepted standards for ambulatory ECG. They are superior to the noble and polarizable metals such as platinum, silver, and gold that induced more signal distortions and are superior to esophageal stainless steel electrodes that corrode in artificial saliva. The study provides rigorous criteria for the selection of electrode materials for prolonged ECG recording by combining long-term in vitro electrode material properties with ECG signal quality assessment.

Solidly Mounted Resonators with Carbon Nanotube Electrodes for Biosensing Applications

The work reported here shows a direct experimental comparison of the sensitivities of AlN solidly mounted resonators (SMR)-based biosensors fabricated with standard metal electrodes and with carbon nanotube electrodes. SMRs resonating at frequencies around 1.75 GHz have been fabricated, some devices using a thin film of multi-wall carbon nanotubes (CNTs) as the top electrode material and some identical devices using a chromium/gold electrode. Protein solutions with different concentrations were loaded on the top of the resonators and their responses to mass-load from physically adsorbed coatings were investigated. Results show that resonators using CNTs as the top electrode material exhibited higher frequency change for a given load due to the higher active surface area of a thin film of interconnecting CNTs compared to that of a metal thin film electrode and hence exhibited greater mass loading sensitivity. It is therefore concluded that the use of CNT electrodes on resonators for their use as gravimetric biosensors is viable and worthwhile.

CMOS integration of AlN based piezoelectric microcantilevers

El gran crecimiento de los sistemas MEMS (Micro Electro Mechanical Systems) así como su presencia en la mayoría de los dispositivos que usamos diariamente despertó nuestro interés. Paralelamente, la tecnología CMOS (Complementary Metal Oxide Semiconductor) es la tecnología más utilizada para la fabricación de circuitos integrados. Además de ventajas relacionadas con el funcionamiento electrónico del dispositivo final, la integración de sistemas MEMS en la tecnología CMOS reduce significantemente los costes de fabricación. Algunos de los dispositivos MEMS con mayor variedad de aplicaciones son los microflejes. Estos dispositivos pueden ser utilizados para la extracción de energía, en microscopios de fuerza atómica o en sensores, como por ejemplo, para biodetección. Los materiales piezoeléctricos más comúnmente utilizados en aplicaciones MEMS se sintetizan a altas temperaturas y por lo tanto no son compatibles con la tecnología CMOS. En nuestro caso hemos usado nitruro de alumino (AlN), que se deposita a temperatura ambiente y es compatible con la tecnología CMOS. Además, es biocompatible, y por tanto podría formar parte de un dispositivo que actúe como biosensor. A lo largo de esta tesis hemos prestado especial atención en desarrollar un proceso de fabricación rápido, reproducible y de bajo coste. Para ello, todos los pasos de fabricación han sido minuciosamente optimizados. Los parámetros de sputtering para depositar el AlN, las distintas técnicas y recetas de ataque, los materiales que actúan como electrodos o las capas sacrificiales para liberar los flejes son algunos de los factores clave estudiados en este trabajo. Una vez que la fabricación de los microflejes de AlN ha sido optimizada, fueron medidos para caracterizar sus propiedades piezoeléctricas y finalmente verificar positivamente su viabilidad como dispositivos piezoeléctricos. ABSTRACT The huge growth of MEMS (Micro Electro Mechanical Systems) as well as their presence in most of our daily used devices aroused our interest on them. At the same time, CMOS (Complementary Metal Oxide Semiconductor) technology is the most popular technology for integrated circuits. In addition to advantages related with the electronics operation of the final device, the integration of MEMS with CMOS technology reduces the manufacturing costs significantly. Some of the MEMS devices with a wider variety of applications are the microcantilevers. These devices can be used for energy harvesting, in an atomic force microscopes or as sensors, as for example, for biodetection. Most of the piezoelectric materials used for these MEMS applications are synthesized at high temperature and consequently are not compatible with CMOS technology. In our case we have used aluminum nitride (AlN), which is deposited at room temperature and hence fully compatible with CMOS technology. Otherwise, it is biocompatible and and can be used to compose a biosensing device. During this thesis work we have specially focused our attention in developing a high throughput, reproducible and low cost fabrication process. All the manufacturing process steps of have been thoroughly optimized in order to achieve this goal. Sputtering parameters to synthesize AlN, different techniques and etching recipes, electrode material and sacrificial layers are some of the key factors studied in this work to develop the manufacturing process. Once the AlN microcantilevers fabrication was optimized, they were measured to characterize their piezoelectric properties and to successfully check their viability as piezoelectric devices.

Synthesis and electrochemical properties of mesoporous nickel oxide

Mesoporous Ni(OH)(2) is synthesized using sodium dodecyl sulfate as a template and urea as a hydrolysis-controlling agent. Mesoporous NiO with a centralized pore-size distribution is obtained by calcining Ni(OH)(2) at different temperatures. The BET specific surface area reaches 477.7 m(2) g(-1) for NiO calcined at 250 degreesC. Structure characterizations indicate a good mesoporous structure for the nickel oxide samples. Cyclic voltammetry shows the NiO to have good capacitive behaviour due to its unique mesoporous structure when using a large amount of NiO to fabricate the electrode. Compared with NiO prepared by dip-coating and cathodic precipitation methods, mesoporous NiO with a controlled pore structure can be used in much larger amounts to fabricate electrodes and still maintain a high specific capacitance and good capacitive behaviour. (C) 2004 Elsevier B.V. All rights reserved.

Synthesis and characterization of mesoporous nickel oxide and its application to electrochemical capacitor

Mesoporous Ni(OH)(2) was synthesized using cationic surfactant as template and urea as hydrolysis-controlling agent. Mesoporous NiO with centralized pore size distribution was obtained by calcining Ni(OH)(2) at different temperatures. The BET specific surface area reaches 477.7 m(2).g(-1) for NiO calcined at 523 K. Structure characterizations indicate the polycrystalline pore wall of mesoporous nickel oxide. The pore-formation mechanism is also deduced to be quasi-reverse micelle mechanism. Cyclic voltammetry shows the good capacitive behavior of these NiO samples due to its unique mesoporous structure when using large amount of NiO to fabricate electrode. Compared with NiO prepared by dip-coating and cathodic precipitation methods, this mesoporous NiO with controlled pore structure can be used in much larger amount to fabricate the electrode and still maintains high specific capacitance and good capacitive behavior.

Synthesis of ordered nanoporous carbon and its application in Li-ion battery

Ordered nanoporous carbon (ONC) was comprehensively tested for the first time as electrode material in lithium-ion battery. Structure characterization shows the order nanoporous structure and tiny crystallite structure of as-synthesized ONC. The electrochemical properties of this carbon were studied by galvanostatic cycling and cyclic voltammetry. Of special interest is that ONC gave no peak on its positive sweep of the cyclic voltammetry, which was different from other known anode materials. Besides, X-ray photoelectron spectroscopy (XPS) and XRD were also used to investigate the electrochemical characteristics of ONC. (c) 2006 Elsevier Ltd. All rights reserved.

Nanodiamond converted hollow graphene spheres as electrodes for supercapacitors

A porous composite formed of hollow graphene spheres with opens in them and amorphous carbon containing nitrogen and oxygenated groups has been fabricated by annealing the mixture of nanodiamond and polyacrylonitrile (PAN). Electrochemical tests on the electrode made of this material show that it may be a promising electrode material for supercapacitors. The relatively high capacitance is mainly attributed to the small inner electrical resistance, the huge specific surface area and the remaining nitrogen and oxygenated groups from the PAN.

Synthesis and characterisation of polyacrylonitrile and its derived carbon materials

Carbon is a versatile material which is composed of different allotropes, and also come in with different structures. Carbon nanofibres (CNFs) is one dimensional carbon nanomaterials, which have exhibited superior mechanical properties, great specific area, good electrical conductivity, good biocompatibility, and ease of modification. In addition to the lower cost associated to compare with carbon nanotubes (CNTs), CNFs have been attracted in numerous applications, such as reinforcement materials, filtrations, Li-ion battery, supercapacitor as well as tissue engineering, just to list a few. Therefore, it is a great deal to understand the relationship between the fabrication conditions and the characteristics of the resulted CNFs. In this project, electrospun PAN NFs were used as precursor material to fabricate carbon nanofibres. In order to produce CNFs with good morphology, the processing parameters of PAN nanofibres by electrospinning was optimized toward to the morphology at solution concentration of 12 wt%. The optimized processing parameters at given concentration were 16 kV, 14 cm and 1.5 mL/h, which led to the formation of PAN NFs with average fibre diameter of approximately 260 nm. Along with the effect of processing parameter study, the effect of concentration on the morphology was also carried out at optimized processing parameters. It was found that by increasing concentration of PAN solution from 2 to 16%, the resulted PAN transformed from beads only, to beaded fibres and finally to smooth fibres. With further increasing concentration the morphology of smooth fibres remain with increase in the fibre diameter. Electrospun PAN NFs with average fibre of 306 nm was selected to be converted into CNFs by using standard heating procedures, stabilisation in air at 280 °C and carbonization in N2. The effect of carbonization temperature ranging from 500 to 1000 °C was investigated, by using SEM, FTIR, Raman, and Impedance spectroscopy. With increasing carbonization temperature from 500 to 1000 °C, the diameter of NFs was decreased from 260 to 187, associated with loss of almost all functional groups of NFs. It was indicated by Raman results, that the graphitic crystallite size was increased from 2.62 to 5.24 nm, and the activation energy obtained for this growth was 7570 J/mol. Furthermore, impedance results (i.e. Cole-Cole plot) revealed that the electrical characteristic of CNFs transitioned from being insulating to electrically conducting in nature, suggested by the different electrical circuits extracted from Cole-Cole plots with carbonization temperature from 500 to 800 °C. The carbonization on PAN NFs with diameter of ~431nm was carried out by using novel route, microwave plasma enhance chemical vapour deposition (MPECVD) process. To compare with carbonized PAN NFs by using conventional route, MPECVD was not only able to facilitate carbonization process, but more interestingly can form carbon nanowalls (CNWs) grown on the surfaces of carbonized PAN NFs. Suggested by the unique morphology, the potential applications for the resulted carbon fibrous hybrid materials are supercapacitor electrode material, filtrations, and etc., The method developed in this project required one step less, compared with other literature. Therefore, using MPECVD on stabilised PAN NFs is proposed as economical, and straightforward approach towards mass production of carbon fibrous hybrid materials containing CNWs.

Avaliação das condições de precipitação do azul da Prússia sobre pó de grafite visando o desenvolvimento de eletrodos de pasta de carbono para a quantificação de nitrito

An amperometric FIA method for nitrite quantification based on nitrite electroreduction and employing a carbon paste electrode (CPE) chemically modified with iron hexacyanoferrate (HCF) as an amperometric detector was developed. The influence of experimental conditions on the preparation of the electrode materials was evaluated and the materials obtained in each study were used for the development of modified electrodes. The electrochemical sensors were prepared by a fast, simple, and inexpensive procedure, and the long-term performance of the electrodes were quite satisfactory as the stability was maintained over one year. HCF was an effective redox mediator for nitrite electroreduction in acidic media, allowing nitrite detection at +0.2 V vs. Ag/AgClsat, which is a potential free of possible interfering species that are normally present in food and water samples. The electrochemical cell used in the FIA system was similar to a batch injection analysis cell, enabling recirculation of the carrier solution. This is an attractive feature because it allows the use of a high flow rate (6 mL min-1) leading to high sensitivity and analysis speed, while keeping reagent consumption low. The proposed method had a detection limit of 9 μmol L-1 and was successfully employed for nitrite quantification in spiked water and sausage samples. The obtained results were in good agreement with those provided by the spectrophotometric official method. At a 95 % confidence level it was not observed statistical differences neither in nitrite content nor in the precision provided by both methods. The experimental conditions for the synthesis of HCF were optimized and the best electrode material was prepared by mixing FeCl3, K4[Fe(CN)6] and carbon powder subjected to an acid and thermal treatment (400 ºC), followed by ultrasonic agitation at 4 °C. This material was used to construct an electrode with improved analytical performance to reduce nitrite, which presented greater stability compared to HCF film electrodeposited on the EPC, showing that the preparation procedure of the electrode material is an effective strategy for the development of HCF modified electrodes.

Effect of the Electrolyte Formulation on the Performances of Edlc and Li-Ion Batteries

One of the most important components in electrochemical storage devices (batteries and supercapacitors) is undoubtedly the electrolyte. The basic function of any electrolyte in these systems is the transport of ions between the positive and negative electrodes. In addition, electrochemical reactions occurring at each electrode/electrolyte interface are the origin of the current generated by storage devices. In other words, performances (capacity, power, efficiency and energy) of electrochemical storage devices are strongly related to the electrolyte properties, as well as, to the affinity for the electrolyte to selected electrode materials. Indeed, the formulation of electrolyte presenting good properties, such as high ionic conductivity and low viscosity, is then required to enhance the charge transfer reaction at electrode/electrolyte interface (e.g. charge accumulation in the case of Electrochemical Double Layer Capacitor, EDLC). For practical and safety considerations, the formulation of novel electrolytes presenting a low vapor pressure, a large liquid range temperature, a good thermal and chemical stabilities is also required.

This lecture will be focused on the effect of the electrolyte formulation on the performances of electrochemical storage devices (Li-ion batteries and supercapacitors). During which, a summary of the physical, thermal and electrochemical data obtained by our group, recently, on the formulation of novel electrolyte-based on the mixture of an ionic liquid (such as EmimNTf2 and Pyr14NTf2) and carbonate or dinitrile solvents will be presented and commented. The impact of the electrolyte formulation on the storage performances of EDLC and Li-ion batteries will be also discussed to further understand the relationship between electrolyte formulation and electrochemical performances. This talk will also be an opportunity to further discuss around the effects of additives (SEI builder: fluoroethylene carbonate and vinylene carbonate), ionic liquids, structure and nature of lithium salt (LiTFSI vs LiPF6) on the cyclability of negative electrode to then enhance the electrolyte formulation. For that, our recent results on TiSnSb and graphite negative electrodes will be presented and discussed, for example 1,2.

1-C. Marino, A. Darwiche1, N. Dupré, H.A. Wilhelm, B. Lestriez, H. Martinez, R. Dedryvère, W. Zhang, F. Ghamouss, D. Lemordant, L. Monconduit “ Study of the Electrode/Electrolyte Interface on Cycling of a Conversion Type Electrode Material in Li Batteries” J. Phys.chem. C, 2013, 117, 19302-19313

2- Mouad Dahbi, Fouad Ghamouss, Mérièm Anouti, Daniel Lemordant, François Tran-Van “Electrochemical lithiation and compatibility of graphite anode using glutaronitrile/dimethyl carbonate mixtures containing LiTFSI as electrolyte” 2013, 43, 4, 375-385.

Surface modifications of nanocrystalline diamond films and their functionalization with phthalocyanines

Boron-doped diamond is a promising electrode material for a number of applications providing efficient carrier transport, a high stability of the electrolytic performance with time, a possibility for dye-sensitizing with photosensitive molecules, etc. It can be functionalized with electron donor molecules, like phthalocyanines or porphyrins, for the development of light energy conversion systems. For effective attachment of such molecules, the diamond surface has to be modified by plasma- or photo-chemical processes in order to achieve a desired surface termination. In the present work, the surface modifications of undoped and boron-doped nanocrystalline diamond (NCD) films and their functionalization with various phthalocyanines (Pcs) were investigated. The NCD films have been prepared by hot filament chemical vapor deposition (HFCVD) on silicon substrates and were thereafter subjected to modifications with O2 or NH3 plasmas or UV/O3 treatments for exchange of the H-termination of the as-grown surface. The effectiveness of the modifications and their stability with time during storage under different ambients were studied by contact angle measurements and X-ray photoelectron spectroscopy (XPS). Furthermore, the surface roughness after the modifications was investigated with atomic force microscopy (AFM) and compared to that of as-grown samples in order to establish the appearance of etching of the surface during the treatment. The as-grown and the modified NCD surfaces were exposed to phthalocyanines with different metal centers (Ti, Cu, Mn) or with different side chains. The results of the Pc grafting were investigated by XPS and Raman spectroscopy. XPS revealed the presence of nitrogen stemming from the Pc molecules and traces of the respective metal atoms with ratios close to those in the applied Pc. In a next step Raman spectra of Ti-Pc, Cu-Pc and Mn-Pc were obtained with two different excitation wavelengths (488 and 785 nm) from droplet samples on Si after evaporation of the solvent in order to establish their Raman fingerprints. The major differences in the spectra were assigned to the effect of the size of the metal ion on the structure of the phthalocyanine ring. The spectra obtained were used as references for the Raman spectra of NCD surfaces grafted with Pc. Finally, selected boron doped NCD samples were used after their surface modification and functionalization with Pc for the preparation of electrodes which were tested in a photoelectrochemical cell with a Pt counter electrode and an Ag/AgCl reference electrode. The light sources and electrolytes were varied to establish their influence on the performance of the dye-sensitized diamond electrodes. Cyclic voltammetry measurements revealed broad electrochemical potential window and high stability of the electrodes after several cycles. The open circuit potential (OCP) measurements performed in dark and after illumination showed fast responses of the electrodes to the illumination resulting in photocurrent generation.

MANIPULATION OF IONS, ELECTRONS, AND PHOTONS IN 2D MATERIALS BY ION INTERCALATION

2D materials have attracted tremendous attention due to their unique physical and chemical properties since the discovery of graphene. Despite these intrinsic properties, various modification methods have been applied to 2D materials that yield even more exciting results. Among all modification methods, the intercalation of 2D materials provides the highest possible doping and/or phase change to the pristine 2D materials. This doping effect highly modifies 2D materials, with extraordinary electrical transport as well as optical, thermal, magnetic, and catalytic properties, which are advantageous for optoelectronics, superconductors, thermoelectronics, catalysis and energy storage applications. To study the property changes of 2D materials, we designed and built a planar nanobattery that allows electrochemical ion intercalation in 2D materials. More importantly, this planar nanobattery enables characterization of electrical, optical and structural properties of 2D materials in situ and real time upon ion intercalation. With this device, we successfully intercalated Li-ions into few layer graphene (FLG) and ultrathin graphite, heavily dopes the graphene to 0.6 x 10^15 /cm2, which simultaneously increased its conductivity and transmittance in the visible range. The intercalated LiC6 single crystallite achieved extraordinary optoelectronic properties, in which an eight-layered Li intercalated FLG achieved transmittance of 91.7% (at 550 nm) and sheet resistance of 3 ohm/sq. We extend the research to obtain scalable, printable graphene based transparent conductors with ion intercalation. Surfactant free, printed reduced graphene oxide transparent conductor thin film with Na-ion intercalation is obtained with transmittance of 79% and sheet resistance of 300 ohm/sq (at 550 nm). The figure of merit is calculated as the best pure rGO based transparent conductors. We further improved the tunability of the reduced graphene oxide film by using two layers of CNT films to sandwich it. The tunable range of rGO film is demonstrated from 0.9 um to 10 um in wavelength. Other ions such as K-ion is also studied of its intercalation chemistry and optical properties in graphitic materials. We also used the in situ characterization tools to understand the fundamental properties and improve the performance of battery electrode materials. We investigated the Na-ion interaction with rGO by in situ Transmission electron microscopy (TEM). For the first time, we observed reversible Na metal cluster (with diameter larger than 10 nm) deposition on rGO surface, which we evidenced with atom-resolved HRTEM image of Na metal and electron diffraction pattern. This discovery leads to a porous reduced graphene oxide sodium ion battery anode with record high reversible specific capacity around 450 mAh/g at 25mA/g, a high rate performance of 200 mAh/g at 250 mA/g, and stable cycling performance up to 750 cycles. In addition, direct observation of irreversible formation of Na2O on rGO unveils the origin of commonly observed low 1st Columbic Efficiency of rGO containing electrodes. Another example for in situ characterization for battery electrode is using the planar nanobattery for 2D MoS2 crystallite. Planar nanobattery allows the intrinsic electrical conductivity measurement with single crystalline 2D battery electrode upon ion intercalation and deintercalation process, which is lacking in conventional battery characterization techniques. We discovered that with a “rapid-charging” process at the first cycle, the lithiated MoS2 undergoes a drastic resistance decrease, which in a regular lithiation process, the resistance always increases after lithiation at its final stage. This discovery leads to a 2- fold increase in specific capacity with with rapid first lithiated MoS2 composite electrode material, compare with the regular first lithiated MoS2 composite electrode material, at current density of 250 mA/g.

Hydrangea-like multi-scale carbon hollow submicron spheres with hierarchical pores for high performance supercapacitor electrodes

Uniform hydrangea-like multi-scale carbon hollow submicron spheres (HCSSg) are fabricated by a simple hydrothermal method using glucose as carbon source and fibrous silicon dioxides spheres as shape guide. Structure characterization suggests that petal-like partially graphitized carbon nanosheets with the thickness of about 10 nm arranged in three dimensions (3D) to form the hydrangea-like hollow spheres (size ranging from 250 to 500 nm) with mesoporous channels, which can be conducive to be a high specific surface area (934 m2 g-1) and bulk density (0.87 cm g-3), hierarchical pores structure with good conductivity. As a result, the HCSSg has been demonstrated to be a supercapacitor electrode material with high gravimetric (386 F g-1 at 0.2 A g-1) and outstanding volumetric (335 F cm-3) capacitance, good rate capability and cycling stability with 94% capacitance retention after 5000 cycles in aqueous electrolytes, thus suggesting its application potential.

Effect of Surface Condition of Electrode on the Surface Melting of Material by Laser-Guided Micro-Arc Discharge

This paper studies the surface melting in the atmosphere by YAG laser-guided micro-arc discharge. In three kinds of surface conditions (free, oiled, and polyethylene covered), we try to control the diameter and the power density of discharge pit. It is found that the power density of 3 x 10(6) W/cm(2) of discharge pit on the oiled surface is moderate to form the melted layer thicker than that of the others, adapting to strengthen the surface of material, and the power density of 1.07 x 10(7) W/cm(2) of discharge pit on the polyethylene-covered surface is highest to form the deepest discharge pit among them, adapting to remove the material.