Polymer-based symmetric electrochromic devices

Abstract The fact that conjugated polymers repeatedly undergo electrochemical doping/undoping processes, which are accompained by color changes, makes these materials very attractive, and much effort has been devoted to their use in advanced devices. There is renewed interest in electroactive polymers that reversibly undergo both p- and n-doping because of their potential application in symmetric electrochemical devices. We employed fused molecules, dithienothiophenes, as monomers to obtain polymers with a narrow band gap suitable for n- and p-doping. The performance results of two symmetric electrochromic devices having as electrodes both poly(dithieno[3,4-b:3',4'-d]thiophene) (pDTT1) and …

Composite Polymer Electrolytes with Improved Lithium Metal Electrode Interfacial Properties: I. Elechtrochemical Properties of Dry PEO‐LiX Systems

Several types of lithium ion conducting polymer electrolytes have been synthesized by hot-pressing homogeneous mixtures of the components, namely, poly(ethylene oxide) (PEO) as the polymer matrix, lithium trifluoromethane sulfonate (LiCF{sub 3}SO{sub 3}), and lithium tetrafluoroborate (LiBF{sub 4}), respectively, as the lithium salt, and lithium gamma-aluminate {gamma}-LiAlO{sub 2}, as a ceramic filler. This preparation procedure avoids any step including liquids so that plasticizer-free, composite polymer electrolytes can be obtained. These electrolyte have enhanced electrochemical properties, such as an ionic conductivity of the order of 10{sup {minus}4} S/cm at 80--90 C and an anodic bre…

Modulation of the Electronic Properties in Polydithienotiiophene Materials

AbstractConjugated polymers with narrow band gap are promising candidates for symmetric electrochemical devices, such as electrochromics and redox supercapacitors, which involve the pand n-doped state of the polymer. Polydithienothiophene materials which are prepared from isomer monomers show this characteristic. The copolymerisation of two dithienothiophene isomers leads to materials whose electronic properties depend on the monomer ratio. Optical and electrochemical characterizations of different copolymers are reported and discussed.

Improved composite materials for rechargeable lithium metal polymer batteries

Abstract The performance of several polymer electrolytes for lithium metal batteries for electric vehicle applications are reported. The best performing electrolyte is the composite PEO 20 LiCF 3 SO 3 –γLiAlO 2 , which was prepared by a solvent-free procedure. It showed coulombic efficiency values of the lithium deposition–stripping process of 94%–96%. Electrochemical tests of lithium polymer battery (LPB) prototypes based on a 3 V LiMn 2 O 4 composite cathode material laminated together with the PEO 20 LiCF 3 SO 3 –γLiAlO 2 electrolyte gave promising results for electric vehicle applications. Even under non-optimized battery design, the prototypes delivered, at the C/3 rate and at 94°C, 40…

SnCo nanowire array as negative electrode for lithium-ion batteries

Abstract Amorphous SnCo alloy nanowires (NWs) grown inside the channels of polycarbonate membranes by potentiostatic codeposition of the two metals (SnCo- PM ) were tested vs. Li by repeated galvanostatic cycles in ethylene carbonate-dimethylcarbonate – LiPF 6 for use as negative electrode in lithium ion batteries. These SnCo electrodes delivered an almost constant capacity value, near to the theoretical for an atomic ratio Li/Sn of 4.4 over more than 35 lithiation–delithiation cycles at 1 C. SEM images of fresh and cycled electrodes showed that nanowires remain partially intact after repeated lithiation–delithiation cycles; indeed, several wires expanded and became porous. Results of amorp…

Toward Tin-Based High-Capacity Anode for Lithium-Ion Battery

Electrochemical deposition of SnCo alloys inside the nanometric pores of commercial membranes is described. Composition, morphology and crystallographic structure of the synthesized nanostructured alloys are reported as well as the results of electrochemical tests carried out both in half-cell and in full battery configuration to investigate the performance of these SnCo alloys as anodes for lithium-ion batteries. Optimized depositions yielded nanostructured alloys that performed 200 deep galvanostatic cycles at C/2 and 30 °C with 80 % capacity retention and coulombic efficiency higher than 97 % after 40 cycles Moreover, charge-discharge rate capability tests showed the high performance of …

Polymer Selection and Cell Design for Electric-Vehicle Supercapacitors

Supercapacitors are devices for applications requiring high operating power levels, such as secondary power sources in electric vehicles (EVs) to provide peak power for acceleration and hill climbing. While electronically conducting polymers yield different redox supercapacitor configurations, devices with the n-doped polymer as the negative electrode and the p-doped polymer as the positive one are the most promising for EV applications. Indeed, this type of supercapacitor has a high operating potential, is able to deliver all the doping charge and, when charged, has both electrodes in the conducting (p- and n-doped) states. This study reports selection criteria for polymer materials and ce…

Nanostructured anode material for Li-ion batteries

The present paper focuses on a nanostructured SnCo alloy electrochemically prepared by template method in view of its use as anode material alternative to graphite in lithium-ion batteries. The fabrication of SnCo nanowire arrays was carried out by potentiostatic co-deposition of the two metals by using nanostructured anodic alumina membranes as template. Electrochemical tests on lithiation-delithiation of these SnCo electrodes in conventional organic electrolyte (EC:DMC LiPF6) at 30°C showed that their specific capacity was stable for about the first 12 cycles at a value near to the theoretical one for Li22Sn5 and, hence, progressively decayed.

Composite polymer electrolytes with improved lithium metal electrode interfacial properties: II. Application in rechargeable batteries

The application of a liquid-free, ceramic-added composite polymer electrolyte in a Li/LiMn{sub 2}O{sub 4} rechargeable battery is presented and discussed. As expected by the high stability of the electrolyte toward the lithium metal anode, the battery has promising characteristics in terms of reliability and cyclability.

New n-dopable thiophene based polymers

Abstract New conjugated polymers containing variable amounts of thienyl and thienyl-S,S-dioxide units have been prepared by chemical or electrochemical polymerization of the appropriate substrates. The presence of the thienyl S,S-dioxide units leads to the decrease of the LUMO energies with respect to those of the ‘all thienyl’ counterparts. Electrochemical and spectro electrochemical data of n-doping of these materials are reported.

Structural and dynamical characterization of melt PEO–salt mixtures

Abstract Salt doped poly ethylene oxide (PEO) mixtures were investigated by means of both small angle neutron scattering and QENS techniques aiming to characterize morphological and dynamical features in the melt state. These experimental evidences provide support to the proposed heterogeneous scenario for polymer electrolytes. In particular, the existence of PEO–cation complexes is proposed to play a major role in intramolecular cooperation and intermolecular transient crosslinks, which affects the mixture properties.

EQCM and Quartz Crystal Impedance Measurements for the Characterization of Thiophene-Based Conducting Polymers

AbstractEQCM was extensively used to investigate ion-transport phenomena during dopingundoping processes of electronically conducting polymers. Several early studies assumed that the polymer films were rigidly coupled to the quartz crystal so as to relate the mass change to the quartz crystal resonant frequency change via the Sauerbrey equation. However, the rigidity of electronically conducting polymer films is doubtful and it has to be demonstrated. Quartz crystal impedance analysis near the resonance is of paramount importance to get insight into the viscoelastic properties of the film [1] and to avoid misleading in the interpretation of EQCM data.This contribution presents and discusses…

Controlling the electronic properties of polythiophene through the insertion of nonaromatic thienyl S,S-dioxide units

A new class of thiophene-based polymers characterized by the presence of one nonaromatic thienyl S,S-dioxide moiety (O) to every two, four, and six aromatic thienyl units (T) was prepared from the newly synthesized precursors TOT, TTOTT, and TTTOTTT, and electrochemically characterized. The polymers displayed remarkably greater electron affinities than that of polythiophene and could be reversibly n-doped at moderate potentials, while still maintaining the property of also being p-doped at moderate potential values. All polymers were characterized by good p-doping/undoping cyclability, while at least four aromatic units to every nonaromatic one were needed to ensure good n-doping/undoping c…

A spectroelectrochemical study of poly(dithienothiophenes)

Abstract The use of n- and p-dopable conjugated polymers as both the working and counter electrodes in an electrochemical device has always attracted chemists and has stimulated the design of new molecules with a low energy gap that can be p- and n-doped efficiently. The present paper reports the spectroelectrochemical study of polymers obtained from several dithienothiophene isomers, molecules with three thiophene rings fused in different positions. Of the six isomers, poly(dithieno[3,4-b:3′,2′-d]thiophene) and poly(dithieno[3,4-b:2′,3′-d] thiophene) were tested against poly(dithieno[3,2-b:2′,3′-d]thiophene) and poly(dithieno[3,4-b:3′,4′-d]thiophene). The differences in their performance, …

Dynamic heterogeneity in polymer electrolytes. Comparison between QENS data and MD simulations

Abstract We have investigated the dynamics of poly(ethylene oxide) (PEO) lithium-based salt electrolytes (PEO–LiBETI) using quasi-elastic neutron scattering (QENS). Measurements were carried out on the spectrometer NEAT (HMI, Berlin) above the melting temperature of PEO ( T m ≈65°C). The experimental data fully support the Molecular Dynamics (MD)-derived model of a heterogeneous dynamics in dilute PEO-salt electrolytes. In agreement with MD simulations carried out on PEO–LiPF 6 , we find evidences for the existence of two dynamic processes: (a) a faster process that is described in terms of the pure PEO dynamics and (b) a second component which we identify with the slower motion of the PEO …

Polydithienothiophenes: Two new conjugated materials with narrow band gap

Abstract The electrochemical polymerisation of dithieno[3,4-b:3',2'-d]thiophene and dithieno[3,4-b:2',3'-d]thiophene leads to conjugated materials with narrow band gap in which the p- and n-doping processes are possible in organic electrolytes. The spectroelectrochemical study of these polymers is reported.

Electronically conducting polymers and activated carbon: Electrode materials in supercapacitor technology

Investigation on lithium/polymer electrolyte interface for high performance lithium rechargeable batteries

Abstract Performance data of several linear and cross-linked polymer electrolytes are reported and the electrochemical criteria for the selection of electrolytes to be used in electric vehicle lithium metal batteries are discussed. Further, laboratory lithium cells with LiMn2O4 composite cathode were tested to ascertain the effective viability of these polymer in solid-state batteries and preliminary results are reported. This study clearly demonstrates the importance of a broad-based electrochemical characterization in selecting an electrolyte for lithium metal batteries.

High-performing Sn-Co nanowire electrodes as anodes for lithium-ion batteries

Abstract The preparation of Sn 2 Co 3 nanowire arrays (NWs) electrogrown inside the channels of polycarbonate membranes and their characterization as anodes for Li-ion batteries both in half-cell vs. Li and in battery configuration are reported. The Sn 2 Co 3 NW electrodes tested by deep galvanostatic charge/discharge cycles in ethylene carbonate-dimethylcarbonate (1:1) – LiPF 6 1 M displayed 80% capacity retention after 200 cycles at C/2 and 30 °C, and a high charge and discharge rate capability at C-rate from C/3 (0.33 A/g) to 10C (10 A/g) at 30° and 10 °C. Electrodes with the highest alloy loading delivered up to 0.6 mAh cm −2 at C/2. The performance of these electrodes in battery config…

Polythiophene S,S dioxides: an investigation on electrochemical doping

Abstract A new strategy for functionalizing oligothiophenes is the transformation of the thienyl sulphurs into the corresponding S,S dioxides, with the effect of lowering the LUMO energy without significantly affecting the HOMO one. From a quinquethiophene S,S dioxide derivative, a polymer (pQTDO) which can be reversibly n-doped at not very negative potentials still maintaining the property of being p-doped at moderate potential values was electrosynthesized. There is, however, a great difference in the ability to store charge of the polymer’s p- and n-doped forms: a great amount of injected negative charge irreversibly modifies the structure of pQTDO.