Multifunctional Carbon Fiber Composites: A Structural, Energy Harvesting, Strain-Sensing Material

Multifunctional structural materials are capable of reducing system level mass and increasing efficiency in load carrying structures. Materials that are capable of harvesting energy from the surrounding environment are advantageous for autonomous electrically powered systems. However, most energy harvesting materials are non-structural and add parasitic mass, reducing structural efficiency. Here, we show a structural energy harvesting composite material consisting of two carbon fiber (CF) layers embedded in a structural battery electrolyte (SBE) with a longitudinal modulus of 100 GPa-almost on par with commercial CF pre-pregs. Energy is harvested through mechanical deformations using the piezo-electrochemical transducer (PECT) effect in lithiated CFs. The PECT effect creates a voltage difference between the two CF layers, driving a current when deformed. A specific power output of 18 nW/g is achieved. The PECT effect in the lithiated CFs is observed in tension and compression and can be used for strain sensing, enabling structural health monitoring with low added mass. The same material has previously been shown capable of shape morphing. The two additional functionalities presented here result in a material capable of four functions, further demonstrating the diverse possibilities for CF/SBE composites in multifunctional applications in the future

Hybrid polymer-liquid lithium ion electrolytes: effect of porosity on the ionic and molecular mobility

Alternative electrolyte systems such as hybrid electrolytes are much sought after to overcome safety issues related to liquid electrolytes in lithium ion batteries (LIBs). Hybrid solid-liquid electrolytes (HEs) like the heterogeneous structural battery electrolyte (SBE) consist of two discrete co-existing phases prepared by polymerization-induced phase separation: one solid polymer phase providing mechanical integrity and the other one a percolating liquid ion-conducting phase. The present work investigates the ion and the solvent mobility in a series of HEs using morphological, electrochemical impedance and NMR spectroscopic methods. All the dried HEs exhibit a porous structure with a broad pore size distribution stretching down to <10 nm diameter. Penetration of the individual components of the solution, that is the ions and the solvent, in the solid polymer phase is demonstrated. Yet, it is the pores that are the main ion conduction channels in the liquid-saturated HEs and, in general, translational mobility is strongly dependent on the volume fraction and size of the pores and, thereby, on the initial liquid electrolyte content. We also observe that the translational mobility of solvent and the ions vary differently with the pore volume fraction. This finding is explained by the presence of small mesopores where the mobility strongly depends on the specific interactions of the molecular constituent with the pore wall. These interactions are inferred to be stronger for the EC/PC solvent than for the ions. This study shows how the morphology and the chemical composition of HEs affect the ionic and molecular transport in the system

Comparison of Oxygen Adsorption and Platinum Dissolution in Acid and Alkaline Solutions Using Electrochemical Quartz Crystal Microbalance

Platinum (Pt) is a widely used electrocatalyst material in fuel cells and electrolysers. Proton exchange membrane (PEM) fuel cells and electrolysis operate under highly acidic conditions whereas the more recently developed anion exchange membrane (AEM) processes take place under alkaline conditions. Pt dissolution and Pt oxidation during operation and varying potentials has been studied mainly for the acidic PEM and less for the alkaline AEM. This study presents a comparison of Pt dissolution and Pt oxidation in 0.5 M H2SO4 and 1 M KOH using electrochemical quartz crystal microbalance (EQCM) on Pt thin films. Physical characterisation using electron microscopy and atomic force microscopy (AFM) revealed small, yet significant differences in the Pt film surface structure, which is related to differences in measured electrochemical surface area (ECSA). The mass increase from adsorption of oxygenated species and Pt oxidation is higher in alkaline conditions compared to in acid while dissolution of Pt is similar

Oxygen reduction reaction kinetics on a Pt thin layer electrode in AEMFC

The study of the catalytic activity in a fuel cell is challenging, as mass transport, gas crossover and the counter electrode are generally interfering. In this study, a Pt electrode consisting of a thin film deposited on the gas diffusion layer was employed to study the oxygen reduction reaction (ORR) in an operating Anion Exchange Membrane Fuel Cell (AEMFC). The 2D Pt electrode was assembled together with a conventional porous Pt/C counter electrode and an extra Pt/C layer and membrane to reduce the H2 crossover. Polarization curves at different O2 partial pressures were recorded and the resulting reproducible ORR activities were normalized with respect to the active surface area (ECSA), obtained by CO stripping. As expected, decreasing the O2 partial pressure results in a negative shift in open circuit voltage (OCV), cell voltage and maximum attainable current density. For cell voltages above 0.8 V a fairly constant Tafel slope of 60 mV dec−1 was recorded but at lower voltages the slope increases rapidly. The observed Tafel slope can be explained by a theoretical model with an associative mechanism where charge- and proton-transfer steps are decoupled, and the proton transfer is the rate-determining step. A reaction order of 1 with respect to O2 was obtained at 0.65 V which corresponds well with the mechanism suggested above. Based on the obtained catalyst activities, the electrode performance is comparable to good porous electrodes found in the field. The methodology presented in this study is expected to be useful in future kinetic studies of other catalysts for AEMFC

A screen-printing method for manufacturing of current collectors for structural batteries

Structural carbon fibre composite batteries are a type of multifunctional batteries that combine the energy storage capability of a battery with the load-carrying ability of a structural material. To extract the current from the structural battery cell, current collectors are needed. However, current collectors are expensive, hard to connect to the electrode material and add mass to the system. Further, attaching the current collector to the carbon fibre electrode must not affect the electrochemical properties negatively or requires time-consuming, manual steps. This paper presents a proof-of-concept method for screen-printing of current collectors for structural carbon fibre composite batteries using silver conductive paste. Current collectors are screen-printed directly on spread carbon fibre tows and a polycarbonate carrier film. Experimental results show that the electrochemical performance of carbon fibre vs lithium metal half-cells with the screen-printed collectors is similar to reference half-cells using metal foil and silver adhered metal-foil collectors. The screen-printed current collectors fulfil the requirements for electrical conductivity, adhesion to the fibres and flexible handling of the fibre electrode. The screen-printing process is highly automatable and allows for cost-efficient upscaling to large scale manufacturing of arbitrary and complex current collector shapes. Hence, the screen-printing process shows a promising route to realization of high performing current collectors in structural batteries and potentially in other types of energy storage solutions

Enhanced oxygen reduction activity with rare earth metal alloy catalysts in proton exchange membrane fuel cells

Alloying platinum is an approach to increase the oxygen reduction reaction (ORR) activity and at the same time reduce the amount of precious platinum catalyst in proton exchange membrane fuel cells (PEMFC). In this work the cathode activity of thin films of rare earth metals (REM) alloys, Pt Y, Pt Gd and Pt Tb, produced by sputter deposition onto gas diffusion layers, are evaluated in a fuel cell by means of polarization curves in O /H , and cyclic- and CO-stripping voltammetry in N /5% H . Prior to evaluation, the model electrodes were acid-treated to obtain a Pt skin covering the PtREM alloy bulk, as was revealed by energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). The core shell alloys of Pt Y and Pt Gd catalysts show a specific activity enhancement at 0.9 V of 2.5 times compared to pure Pt. The slightly lower enhancement factor of 2.0 for Pt Tb is concluded to be due to leaching of the REM, that resulted in a thicker, and subsequently less strained, Pt overlayer. The high activity, combined with the minor changes in surface composition, achieved in the fuel cell environment shows that PtREM core shell catalysts are promising for the cathode reaction in PEMFC

Realisation of structural battery composite materials

This paper introduces the concept of structural battery composite materials and their possibledevices and the rationale for developing them. The paper presents an overview of the researchperformed in Sweden on a novel structural battery composite material. The research areas addressedinclude: carbon fibre electrodes, structural separators, multifunctional matrix materials, devicearchitectures and material functionalization. Material characterization, fabrication and validation arealso discussed. The paper focuses on a patented battery composite material technology. Here, carbonfibres are employed as combined negative battery electrodes and reinforcement, coated with a solidpolymer electrolyte working simultaneously as electrolyte and separator with ability to transfermechanical loads. The coated fibres are distributed in a conductive positive cathode material on analuminium electron collector film. Efficient Li-ion transport between the electrodes is achieved by thesolid polymer electrolyte coating being only a few hundred nanometres thick.Finally some outstanding scientific and engineering challenges are discussed. Such challenges,calling for further research are related to manufacture, development of new solid polymer electrolytesfor improved multifunctionality and the lack of material models

Characterization of the Mass-Transport Phenomena in a Superconcentrated LiTFSI:Acetonitrile Electrolyte

Superconcentration of aprotic electrolytes has recently emerged as a way to stabilize solvents that otherwise would be impossible to use, in e.g. lithium-ion batteries (LIBs). As demanding applications, such as hybrid electric vehicles and fast charging, become increasingly important, battery manufacturers are struggling to find a suitable electrolyte able to deliver high power with low polarization. Electrolyte characterizations able to accurately predict the high-power performance of such electrolytes are also of utmost importance. This study reports a full.characterization of the mass-transport phenomena for a superconcentrated LiTFSL-acetonitrile electrolyte in concentrations ranging from 2.7 M to 4.2 M. The method obtains the ionic conductivity, cationic transport number, diffusion coefficient, and the thermodynamic enhancement factor, by combining mathematical modeling and three electrochemical experiments. Furthermore, the density and the viscosity were measured. The transport number with respect to the room is found to be very high compared to other liquid LIB electrolytes, but a low diffusion coefficient lowers overall performance. The ionic conductivity decreases quickly with concentration, dropping from 12.7 mS/cm at 2.7 M to 0.76 mS/cm at 4.2 M. Considering all the effects in terms of the mass-transport of the electrolyte, the lower end of the studied concentration range is favorable

On the influence of Pt particle size on the PEMFC cathode performance

Colloidal suspensions of almost spherical and crystalline Pt nanoparticles between 1.6 and 2.6 nm in diameter and with narrow size distribution were synthesized using the phase transfer method (PTM) with alkylamines, C n NH 2 , as stabilizing agents. Batches of such homogenous Pt-C n NH 2 (n = 8, 12) nanocrystals were deposited onto Vulcan XC-72 carbon powder, and the activity for the oxygen reduction reaction (ORR) of this series of Pt/C materials was evaluated under PEMFC conditions. The aim was to elucidate whether this type of stabilized Pt nanoparticles were as active for the ORR as a corresponding commercial Pt/C material, and if any difference in mass activity could be observed between catalysts with different Pt particle size. In the PEMFC experiments, i.e. voltammetry in oxygen and nitrogen, it was found that, after an initial electrode activation, the ORR activity of the catalysts prepared from the alkylamine-stabilized Pt nanoparticles deposited on carbon was as high as that of the employed commercial reference catalyst. In fact, all samples in the Pt/C series showed high and very similar ORR activity normalized to Pt-loading, without significant dependence on the initial Pt particle size. However, pre- and post-electrochemical characterization of the Pt/C material series with TEM showed that structural changes of the Pt nanoparticles occurred during electrochemical evaluation. In all samples studied the mean Pt particle size increased during the electrochemical evaluation resulting in decreased differences between the samples explaining the observed similar ORR performance of the different materials. These results emphasize the necessity of post-operation characterization of fuel cell catalysts when discussing electrocatalytic activity. In addition, employing complex preparation efforts for lowering the Pt particle size below 3 nm may have limited practical value unless the particles are stabilized from electrochemical sintering. \ua9 2007 Elsevier Ltd. All rights reserved

Evaluation of TiO2 as catalyst support in Pt-TiO2/C composite cathodes for the proton exchange membrane fuel cell

Anatase TiO 2 is evaluated as catalyst support material in authentic Pt-TiO 2 /C composite gas diffusion electrodes (GDEs), as a different approach in the context of improving the proton exchange membrane fuel cell (PEMFC) cathode stability. A thermal stability study shows high carbon stability as Pt nanoparticles are supported on TiO 2 instead of carbon in the Pt-TiO 2 /C composite material, presumably due to a reduced direct contact between Pt and C. The performance of Pt-TiO 2 /C cathodes is investigated electrochemically in assembled membrane-electrode assemblies (MEAs) considering the added carbon fraction and Pt concentration deposited on TiO 2 . The O 2 reduction current for the Pt-TiO 2 alone is expectedly low due to the low electronic conductivity in bulk TiO 2 . However, the Pt-TiO 2 /C composite cathodes show enhanced fuel cell cathode performance with growing carbon fraction and increasing Pt concentration deposited on TiO 2 . The proposed reasons for these observations are improved macroscopic and local electronic conductivity, respectively. Electron micrographs of fuel cell tested Pt-TiO 2 /C composite cathodes illustrate only a minor Pt migration in the Pt-TiO 2 /C structure, in which anatase TiO 2 is used as Pt support. On the whole, the study demonstrates a stable Pt-TiO 2 /C composite material possessing a performance comparable to conventional Pt-C materials when incorporated in a PEMFC cathode. \ua9 2008 Elsevier B.V. All rights reserved