Down, Michael P.; Martinez-Perinan, Emiliano; Foster, Christopher W.; Lorenzo, Encarnacion; Smith, Graham C.; Banks, Craig E. (Wiley, 2019-02-10)
The first entirely AM/3D-printed sodium-ion (full-cell) battery is reported herein, presenting a paradigm shift in the design and prototyping of energy- storage architectures. AM/3D-printing compatible composite materials are developed for the first time, integrating the active materials NaMnO2 and TiO2 within a porous supporting material, before being AM/3D- printed into a proof-of-concept model based upon the basic geometry of commercially existing AA battery designs. The freestanding and completely AM/3D-fabricated device demonstrates a respectable performance of 84.3 mAh g-1 with a current density of 8.43 mA g-1; note that the structure is typically comprised of 80% thermoplastic, but yet, still works and functions as an energy-storage platform. The AM/3D-fabricated device is critically benchmarked against a battery developed using the same active materials, but fabricated via a traditional manufacturing method utilizing an ink-based/doctor-bladed methodology, which is found to exhibit a specific capacity of 98.9 mAh m-2 (116.35 mAh g-1). The fabrication of fully AM/3D-printed energy-storage architectures compares favorably with traditional approaches, with the former providing a new direction in battery manufacturing. This work represents a paradigm shift in the technological and design considerations in battery and energy-storage architectures
Kettle, Jeff; Waters, Huw; Horie, Masaki; Smith, Graham C. (IOP Publishing, 2016-01-27)
The use of processing additives is known to accelerate the degradation of Organic Photovoltaics (OPVs) and therefore, this paper studies the impact of selecting alternative processing additives for PCPDTBT:PC71BM solar cells in order to improve the stability. The use of naphthalene-based processing additives has been undertaken, which is shown to reduce the initial power conversion efficiency by 23%-42%, primarily due to a decrease in the short-circuit current density, but also fill factor. However, the stability is greatly enhanced by using such additives, with the long term stability (T50%) enhanced by a factor of four. The results show that there is a trade-off between initial performance and stability to consider when selecting the initial process additives. XPS studies have provided some insight into the decreased degradation and show that using 1-chloronaphthalene (ClN) leads to reduced morphology changes and reduced oxidation of the thiophene-ring within the PCPDTBT backbone.
The chemical degradation of the Poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] or ‘ PTB7’ has been studied using X-ray Photoelectron Spectroscopy (XPS). This material system appears to be intrinsically unstable especially when illuminated in air and XPS studies confirm the rapid photo-degradation is related to changes in chemical structure of the polymer. In particular, XPS spectra show an initial reduction in relative C-C intensity, suggests loss of the alkoxy side chains. This is followed by a dramatic increase in the level of oxygen-bonded species, especially C-O at ~286.5 eV and C(=O)O at 289.2 eV, indicative of COOH and OH group formation, and oxidation of S. The XPS results support the view that using processing additives reduces the chemical stability of the polymer and provides insight into strategies to improve molecular design to ensure higher chemical stability.
A mismatch in bone and implant elastic modulus can lead to aseptic loosening and ultimately implant failure. Selective elemental composition of titanium (Ti) alloys coupled with surface treatment can be used to improve osseointegration and reduce bacterial adhesion. The biocompatibility and antibacterial properties of Ti-35Nb-7Zr-6Ta (TNZT) using fibre laser surface treatment were assessed in this work, due to its excellent material properties (low Young’s modulus and non-toxicity) and the promising attributes of fibre laser treatment (very fast, non-contact, clean and only causes changes in surface without altering the bulk composition/microstructure). The TNZT surfaces in this study were treated in a high speed regime, specifically 100 and 200 mm/s, (or 6 and 12 m/min). Surface roughness and topography (WLI and SEM), chemical composition (SEM-EDX), microstructure (XRD) and chemistry (XPS) were investigated. The biocompatibility of the laser treated surfaces was evaluated using mesenchymal stem cells (MSCs) cultured in vitro at various time points to assess cell attachment (6, 24 and 48 h), proliferation (3, 7 and 14 days) and differentiation (7, 14 and 21 days). Antibacterial performance was also evaluated using Staphylococcus aureus (S. aureus) and Live/Dead staining. Sample groups included untreated base metal (BM), laser treated at 100 mm/s (LT100) and 200 mm/s (LT200). The results demonstrated that laser surface treatment creates a rougher (Ra value of BM is 199 nm, LT100 is 256 nm and LT200 is 232 nm), spiky surface (Rsk > 0 and Rku > 3) with homogenous elemental distribution and decreasing peak-to-peak distance between ripples (0.63 to 0.315 m) as the scanning speed increases (p < 0.05), generating a surface with distinct micron and nano scale features. The improvement in cell spreading, formation of bone-like nodules (only seen on the laser treated samples) and subsequent four-fold reduction in bacterial attachment (p < 0.001) can be attributed to the features created through fibre laser treatment, making it an excellent choice for load bearing implant applications. Last but not least, the presence of TiN in the outermost surface oxide might also account for the improved biocompatibility and antibacterial performances of TNZT.
Brownson, Dale A. C.; Smith, Graham C.; Banks, Craig E. (The Royal Society, 2017-11-15)
The modification of electrode surfaces is widely implemented in order to try and improve electron transfer kinetics and surface interactions, most recently using graphene related materials. Currently, the use of ‘as is’ graphene oxide (GO) has been largely overlooked, with the vast majority of researchers choosing to reduce GO to graphene or use it as part of a composite electrode. In this paper, ‘as is’ GO is explored and electrochemically characterized using a range of electrochemical redox probes, namely potassium ferrocyanide(II), N,N,N ,N -tetramethyl-p-phenylenediamine (TMPD), dopamine hydrochloride and epinephrine. Furthermore, the electroanalytical efficacy of GO is explored towards the sensing of dopamine hydrochloride and epinephrine via cyclic voltammetry. The electrochemical response of GO is benchmarked against pristine graphene and edge plane-/basal plane pyrolytic graphite (EPPG and BPPG respectively) alternatives, where the GO shows an enhanced electrochemical/electroanalytical response. When using GO as an electrode material, the electrochemical response of the analytes studied herein deviate from that expected and exhibit altered electrochemical responses. The oxygenated species encompassing GO strongly influence and dominate the observed voltammetry, which is crucially coverage dependent. GO electrocatalysis is observed, which is attributed to the presence of beneficial oxygenated species dictating the response in specific cases, demonstrating potential for advantageous electroanalysis to be realized. Note however, that crucial coverage based regions are observed at GO modified electrodes, owing to the synergy of edge plane sites and oxygenated species. We report the true beneficial electrochemistry of GO, which has enormous potential to be beneficially used in various electrochemical applications ‘as is’ rather than be simply used as a precursor to making graphene and is truly a fascinating member of the graphene family
Rowley-Neale, Samuel J.; Foster, Christopher W.; Smith, Graham C.; Brownson, Dale A. C.; Banks, Craig E. (Royal Society of Chemistry, 2017-01-25)
We demonstrate a facile, low cost and reproducible methodology for the production of electrocatalytic 2D-MoSe2 incorporated/bulk modified screen-printed electrodes (MoSe2-SPEs). The MoSe2-SPEs outperform traditional carbon based electrodes, in terms of their electrochemical activity, towards the Hydrogen Evolution Reaction (HER). The electrocatalytic behaviour towards the HER of the 2D-MoSe2 within the fabricated electrodes is found to be mass dependent, with an optimal mass ratio of 10% 2D-MoSe2 to 90% carbon ink. MoSe2-SPEs with this optimised ratio exhibit a HER onset, Tafel value and a turn over frequency of ca. −460 mV (vs. SCE), 47 mV dec−1 and 1.48 respectively. These values far exceed the HER performance of graphite (unmodified) SPEs, that exhibit a greater electronegative HER onset and Tafel value of ca. −880 mV and 120 mV dec−1 respectively. It is clear that impregnation of 2D-MoSe2 into the MoSe2-SPEs bulk ink/structure significantly increases the performance of SPEs with respect to their electrocatalytic activity towards the HER. When compared to SPEs that have been modified via a drop-casting technique, the fabricated MoSe2-SPEs exhibit excellent cycling stability. After 1000 repeat scans, a 10% modified MoSe2-SPE displayed no change in its HER onset potential of −450 mV (vs. SCE) and an increase of 31.6% in achievable current density. Conversely, a SPE modified via drop-casting with 400 mg cm−2 of 2D-MoSe2 maintained its HER onset potential of −480 mV (vs. SCE), however exhibited a 27.4% decrease in its achievable current density after 1000 scans. In addition to the clear performance benefits, the production of MoSe2-SPEs mitigates the need to post hoc modify an electrode via the drop-casting technique. We anticipate that this facile production method will serve as a powerful tool for future studies seeking to utilise 2D materials in order to mass-produce SPEs/surfaces with unique electrochemical properties whilst providing substantial stability improvements over the traditionally utilised technique of drop-casting.
Kettle, Jeff; Waters, Huw; Ding, Ziqian; Smith, Graham C. (2015-04-20)
Analysis of the degradation routes for PCPDTBT-based solar cells under illumination and in the presence of air have been conducted using a combination of X-ray Photoelectron Spectroscopy (XPS), Time-Of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) and solar cell device data. After ageing, XPS studies show that PCPDTBT appears as an oxygen-containing polymer, with data indicating that a break-up in the aromatic rings, formation of sulphates at the thiophene ring, chain scission in the polymer backbone and also loss of side chains. XPS studies on active layers blends of PCPDTBT and PCBM also show significant changes in the vertical composition during ageing, with increased enrichment of PCPDTBT observed at the top surface and that the use of a processing additive (ODT) has a negative impact on the morphological stability. TOF-SIMS has been used to study electrode degradation during ageing experiments leads to migration of indium and tin ions into the active layer in non-inverted devices, but is eliminated for inverted devices.
Galdino, Flávia E.; Smith, Jamie P.; Kwamou, Sophie I.; Kampouris, Dimitrios K.; Iniesta, Jesus; Smith, Graham C.; Bonacin, Juliano A.; Banks, Craig E. (American Chemical Society, 2015-11-12)
A reagentless pH sensor based upon disposable and economical graphite screen-printed electrodes (GSPEs) is demonstrated for the first time. The voltammetric pH sensor utilises GSPEs which are chemically pre-treated to form surface immobilised oxygenated species that when their redox behaviour is monitored, give a Nernstian response over a large pH range (1-13). An excellent experimental correlation is observed between the voltammetric potential and pH over the entire pH range of 1-13, such a response is not usually expected but rather deviation from linearity is encountered at alkaline pH values; absence of this has previously been attributed to a change in pKa value of surface immobilised groups. This non-deviation, which is observed here in the case of our facile produced reagentless pH sensor and also reported in the literature for pH sensitive compounds immobilized upon carbon electrodes/surfaces,where a linear response is observed over the entire pH range, is explained alternatively for the first time. The performance of the GSPE pH sensor is directly compared with a glass pH probe and applied to the measurement of pH in real samples where an excellent correlation between the two protocols is observed validating the proposed GSPE pH sensor.
Rowley-Neale, Samuel J.; Smith, Graham C.; Banks, Craig E. (American Chemical Society, 2017-06-02)
Two-dimensional molybdenum disulfide (2D-MoS2) screen-printed electrodes (2D-MoS2-SPEs) have been designed, fabricated, and evaluated toward the electrochemical oxygen reduction reaction (ORR) within acidic aqueous media. A screen-printable ink has been developed that allows for the tailoring of the 2D-MoS2 content/mass used in the fabrication of the 2D-MoS2-SPEs, which critically affects the observed ORR performance. In comparison to the graphite SPEs (G-SPEs), the 2D-MoS2-SPEs are shown to exhibit an electrocatalytic behavior toward the ORR which is found, critically, to be reliant upon the percentage mass incorporation of 2D-MoS2 in the 2D-MoS2-SPEs; a greater percentage mass of 2D-MoS2 incorporated into the 2D-MoS2-SPEs results in a significantly less electronegative ORR onset potential and a greater signal output (current density). Using optimally fabricated 2D-MoS2-SPEs, an ORR onset and a peak current of approximately +0.16 V [vs saturated calomel electrode (SCE)] and −1.62 mA cm–2, respectively, are observed, which exceeds the −0.53 V (vs SCE) and −635 μA cm–2 performance of unmodified G-SPEs, indicating an electrocatalytic response toward the ORR utilizing the 2D-MoS2-SPEs. An investigation of the underlying electrochemical reaction mechanism of the ORR within acidic aqueous solutions reveals that the reaction proceeds via a direct four-electron process for all of the 2D-MoS2-SPE variants studied herein, where oxygen is electrochemically favorably reduced to water. The fabricated 2D-MoS2-SPEs are found to exhibit no degradation in the observed achievable current over the course of 1000 repeat scans. The production of such inks and the resultant mass-producible 2D-MoS2-SPEs mitigates the need to modify post hoc an electrode via the drop-casting technique that has been previously shown to result in a loss of achievable current over the course of 1000 repeat scans. The 2D-MoS2-SPEs designed, fabricated, and tested herein could have commercial viability as electrocatalytic fuel cell electrodes because of being economical as a result of their scales of economy and inherent tailorability. The technique utilized herein to produce the 2D-MoS2-SPEs could be adapted for the incorporation of different 2D nanomaterials, resulting in SPEs with the inherent advantages identified above.
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