Performance analysis of solution-processed nanosheet strain sensors-a systematic review of graphene and MXene wearable devices.

Nanotechnology has led to the realisation of many potentialInternet of Thingsdevices that can be transformative with regards to future healthcare development. However, there is an over saturation of wearable sensor review articles that essentially quote paper abstracts without critically assessing the works. Reported metrics in many cases cannot be taken at face value, with researchers overly fixated on large gauge factors. These facts hurt the usefulness of such articles and the very nature of the research area, unintentionally misleading those hoping to progress the field. Graphene and MXenes are arguably the most exciting organic and inorganic nanomaterials for polymer nanocomposite strain sensing applications respectively. Due to their combination of cost-efficient, scalable production and device performances, their potential commercial usage is very promising. Here, we explain the methods for colloidal nanosheets suspension creation and the mechanisms, metrics and models which govern the electromechanical properties of the polymer-based nanocomposites they form. Furthermore, the many fabrication procedures applied to make these nanosheet-based sensing devices are discussed. With the performances of 70 different nanocomposite systems from recent (post 2020) publications critically assessed. From the evaluation of these works using universal modelling, the prospects of the field are considered. Finally, we argue that the realisation of commercial nanocomposite devices may in fact have a negative effect on the global climate crisis if current research trends do not change.

Exotic Electronic Properties of 2D Nanosheets Isolated from Liquid Phase Exfoliated Phyllosilicate Minerals.

Spectrally inactive, electrically insulating, and chemically inert are adjectives broadly used to describe phyllosilicate minerals like mica and chlorite. Here, the above is disproved by demonstrating aqueous suspensions of liquid exfoliated nanosheets from five bulk mica types and chlorite schist. Nanosheet quality is confirmed via transmission electron and X-ray photoelectron spectroscopies, as well as electron diffraction. Through Raman spectroscopy, a previously unreported size- and layer-dependent spectral fingerprint is observed. When analyzing the high-yield suspensions (≈1 mg mL-1 ) through UV-vis spectroscopy, all phyllosilicates present bandgap (Eg ) narrowing from ≈7 eV in the bulk to ≈4 eV for monolayers. Unusually, the bandgap is inversely proportional to the areal size (A) of the nanosheets, measured via atomic force microscopy. Due to an unrecorded quantum confinement effect, nanosheet electronic properties scale toward semiconducting behavior (bandgap ≈3 eV) as nanosheet area increases. Furthermore, modeling X-ray diffraction spectra shows that the root cause of the initial bandgap narrowing is lattice relaxation. Finally, with their broad range of isomorphically substituted ions, phyllosilicate nanosheets show remarkable catalytic properties for hydrogen production.

Piezoresistive Fibers with Large Working Factors for Strain Sensing Applications.

Piezoresistive fibers with large working factors remain of great interest for strain sensing applications involving large strains, yet difficult to achieve. Here, we produced strain-sensitive fibers with large working factors by dip-coating nanocomposite piezoresistive inks on surface-modified polyether block amide (PEBA) fibers. Surface modification of neat PEBA fibers was carried out with polydopamine (PDA) while nanocomposite conductive inks consisted of styrene-ethylene-butylene-styrene (SEBS) elastomer and carbon black (CB). As such, the deposition of piezoresistive coatings was enabled through nonconventional hydrogen-bonding interactions. The resultant fibers demonstrated well-defined piezoresistive linear relationships, which increased with CB filler loading in SEBS. In addition, gauge factors decreased with increasing CB mass fractions from ∼15 to ∼7. Furthermore, we used the fatigue theory to predict the endurance limit (Ce) of our fibers toward resistance signal stability. Such a piezoresistive performance allowed us to explore the application of our fibers as strain sensors for monitoring the movement of finger joints.

Highly Sensitive Composite Foam Bodily Sensors Based on the g-Putty Ink Soaking Procedure.

Electrically conductive composite materials are highlighted as a potential tech path toward future flexible devices for wearable health technologies. To be commercially viable, these materials must not only be mechanically soft, highly sensitive to deformation, and report a sustainable signal but also utilize manufacturing methods that facilitate large-scale production. An ideal candidate for these envisioned technologies is the viscous, electromechanically sensitive composite material g-putty. Inks based on g-putty here are shown to transform a commercial polymer foam into a sensitive strain sensing material through a simple, scalable soaking procedure. Foam composites reported here have sensitives as high as ∼20 in terms of compressive strain and ∼0.4 kPa-1 with respect to applied compressive stress; both values being comparable to the parent g-putty material. Through g-putty's self-adhering nature, the foams used acted as an elastic scaffolding that aided in overcoming many of the hysteresis effects associated with g-putty without the need for further encapsulation methods. From this, these composite foams were demonstrated to have a sustainable signal that allowed for effective impact and vital sign sensing.

Printable G-Putty for Frequency- and Rate-Independent, High-Performance Strain Sensors.

While nanocomposite electromechanical sensors are expected to display reasonable conductivity and high sensitivity, little consideration is given to eliminating hysteresis and strain rate/frequency dependence from their response. For example, while G-putty, a composite of graphene and polysiloxane, has very high electromechanical sensitivity, its extreme viscoelasticity renders it completely unsuitable for real sensors due to hysteretic and rate-/frequency-dependent effects. Here it is shown that G-putty can be converted to an ink and printed into patterned thin films on elastic substrates. A partial graphene-polymer phase segregation during printing increases the thin-film conductivity by ×106 compared to bulk, while the mechanical effects of the substrate largely suppress hysteresis and completely remove strain rate and frequency dependence. This allows the fabrication of practical, high-gauge-factor, wearable sensors for pulse measurements as well as patterned sensors for low-signal vibration sensing.

Low cost, high performance ultrafiltration membranes from glass fiber-PTFE-graphene composites.

The development of low-cost ultrafiltration membranes with relatively high flow rate and selectivity is an important goal which could improve access to clean water in the developing world. Here we demonstrate a method to infuse mixtures of graphene nanosheets and Teflon nanoparticles into ultra-cheap glass fibre membranes. Annealing the resultant composites leads to coalescence of the Teflon, resulting in very stable membranes with significantly enhanced mechanical properties. In filtration tests, while adding ~ 10 wt% graphene/Teflon to the glass fibre membrane decreased the flow rate by × 100, the selectivity improved by × 103 compared to the neat glass fibre membrane. This combination of selectively and flow rate was significantly better than any commercial membrane tested under similar circumstances. We found these membranes could remove > 99.99% of 25-250 nm diameter SiC nanoparticles dispersed in ethanol, transmitting only particles with diameters < 40 nm, performance which is superior to commercial alumina membranes. Field trials on dirty canal water showed these composite membranes to remove aluminium to a level × 10 below the EU limit for drinking water and reduce iron and bacteria contents to below detectable levels.

Stumbling through the Research Wilderness, Standard Methods To Shine Light on Electrically Conductive Nanocomposites for Future Healthcare Monitoring.

Electrically conductive nanocomposites are an exciting ever-expanding area of research that has yielded many versatile technologies for wearable health devices. Acting as strain-sensing materials, real-time medical diagnostic tools based on these materials may very well lead to a golden age of healthcare. Currently, the goal in research is to create a material that simultaneously has both a large gauge factor (G) and sensing range. However, a weakness in the area of electromechanical research is the lack of standardization in the reporting of the figure of merit (i.e., G) and the need for other intrinsic metrics to give researchers a more complete view of the research landscape of resistive-type sensors. A paradigm shift in the way in which data are reported is required, to push research in the right direction and to facilitate achieving research goals. Here, we report a standardized method for reporting strain-sensing performance and the introduction of the working factor (W) and the Young's modulus (Y) of a material as figures of merit for sensing materials. Using this standard method, we can define the benchmarks for an optimum sensing material (G > 7, W > 1, Y < 300 kPa) using limits set by standard commercial materials and the human body. Using extrapolated data from 200 publications normalized to this standard method, we can review what composite types meet these benchmark limits, what governs composite performances, the literary trends in composites, and the future prospects of research.

Negative Gauge Factor Piezoresistive Composites Based on Polymers Filled with MoS2 Nanosheets.

Nanocomposite strain sensors, particularly those consisting of polymer-graphene composites, are increasingly common and are of great interest in the area of wearable sensors. In such sensors, application of strain yields an increase in resistance due to the effect of deformation on interparticle junctions. Typically, widening of interparticle separation is thought to increase the junction resistance by reducing the probability of tunnelling between conducting particles. However, an alternative approach would be to use piezoresistive fillers, where an applied strain modifies the intrinsic filler resistance and so the overall composite resistance. Such an approach would broaden sensing capabilities, as using negative piezoresistive fillers could yield strain-induced resistance reductions rather than the usual resistance increases. Here, we introduce nanocomposites based on polyethylene oxide (PEO) filled with MoS2 nanosheets. Doping of the MoS2 by the PEO yields nanocomposites which are conductive enough to act as sensors, while efficient stress transfer leads to nanosheet deformation in response to an external strain. The intrinsic negative piezoresistance of the MoS2 leads to a reduction of the composite resistance on the application of small tensile strains. However, at higher strain the resistance grows due to increases in junction resistance. MoS2-PEO composite gauge factors are approximately -25 but fall to -12 for WS2-PEO composites and roughly -2 for PEO filled with MoSe2 or WSe2. We develop a simple model, which describes all these observations. Finally, we show that these composites can be used as dynamic strain sensors.

High capacity silicon anodes enabled by MXene viscous aqueous ink.

The ever-increasing demands for advanced lithium-ion batteries have greatly stimulated the quest for robust electrodes with a high areal capacity. Producing thick electrodes from a high-performance active material would maximize this parameter. However, above a critical thickness, solution-processed films typically encounter electrical/mechanical problems, limiting the achievable areal capacity and rate performance as a result. Herein, we show that two-dimensional titanium carbide or carbonitride nanosheets, known as MXenes, can be used as a conductive binder for silicon electrodes produced by a simple and scalable slurry-casting technique without the need of any other additives. The nanosheets form a continuous metallic network, enable fast charge transport and provide good mechanical reinforcement for the thick electrode (up to 450 µm). Consequently, very high areal capacity anodes (up to 23.3 mAh cm-2) have been demonstrated.

Graphene-coated polymer foams as tuneable impact sensors.

The use of graphene-based nanocomposites as electromechanical sensors has been broadly explored in recent times with a number of papers describing porous, foam-like composites. However, there are no reported foam-based materials that are capable of large dynamic compressive load measurements and very few studies on composite impact sensing. In this work, we describe a simple method of infusing commercially-available foams with pristine graphene to form conductive composites, which we refer to as G-foam. Displaying a strain-dependent electrical response, G-foam was found to be a reasonably effective pressure sensing material. More interestingly, G-foam is a sensitive impact-sensing material. Through the addition of various amounts of polymer filler, the mechanical properties of the composites can be tuned leading to the controllable variation of the impact sensing range. We have developed a simple model which quantitatively explains all our impact sensing data.

Surface coatings of silver nanowires lead to effective, high conductivity, high-strain, ultrathin sensors.

Integrated sensors for bodily measurements require a sensing material that is highly conductive, flexible, thin and sensitive. It is important that these materials are non-invasive in application but robust in nature to allow for effective, continuous measurement. Herein, we report a comparative study of two simple, scalable methods to produce silver nanowire (AgNW) polyurethane (PU) composite materials: layer-by-layer (LBL) and mixed filtration. Both types of composites formed were ultrathin (∼50 µm) and highly conductive (104 S m-1), with the LBL method ultimately found to be superior due to its low percolation threshold. Electrical resistance of the LBL composites was found to vary with strain, making these materials suitable for strain sensing. LBL composites displayed a working strain up to ∼250% and a high gauge factor (G), with values of G ∼70 reported. The sensors reported here were ∼109-times more conductive and ∼104-times thinner than their carbon-based composite sensor counterparts with similar gauge factor. This made the strain sensors presented here among one of the most flexible, highly sensitive, thinnest, conductive materials in literature. We demonstrated that with these properties, the LBL composites formed were ideal for bodily motion detection.

Enabling Flexible Heterostructures for Li-Ion Battery Anodes Based on Nanotube and Liquid-Phase Exfoliated 2D Gallium Chalcogenide Nanosheet Colloidal Solutions.

2D metal chalcogenide (MC) nanosheets (NS) have displayed high capacities as lithium-ion battery (LiB) anodes. Nevertheless, their complicated synthesis routes coupled with low electronic conductivity greatly limit them as promising LiB electrode material. Here, this work reports a facile single-walled carbon nanotube (SWCNT) percolating strategy for efficiently maximizing the electrochemical performances of gallium chalcogenide (GaX, X = S or Se). Multiscaled flexible GaX NS/SWCNT heterostructures with abundant voids for Li+ diffusion are fabricated by embedding the liquid-exfoliated GaX NS matrix within a SWCNT-percolated network; the latter improves the electron transport and ion diffusion kinetics as well as maintains the mechanical flexibility. Consequently, high capacities (i.e., 838 mAh g-1 per gallium (II) sulfide (GaS) NS/SWCNT mass and 1107 mAh g-1 per GaS mass; the latter is close to the theoretical value) and good rate capabilities are achieved, which can be majorly attributed to the alloying processes of disordered Ga formed after the first irreversible GaX conversion reaction, as monitored by in situ X-ray diffraction. The presented approach, colloidal solution processing of SWCNT and liquid-exfoliated MC NS to produce flexible paper-based electrode, could be generalized for wearable energy storage devices with promising performances.

Sensitive electromechanical sensors using viscoelastic graphene-polymer nanocomposites.

Despite its widespread use in nanocomposites, the effect of embedding graphene in highly viscoelastic polymer matrices is not well understood. We added graphene to a lightly cross-linked polysilicone, often encountered as Silly Putty, changing its electromechanical properties substantially. The resulting nanocomposites display unusual electromechanical behavior, such as postdeformation temporal relaxation of electrical resistance and nonmonotonic changes in resistivity with strain. These phenomena are associated with the mobility of the nanosheets in the low-viscosity polymer matrix. By considering both the connectivity and mobility of the nanosheets, we developed a quantitative model that completely describes the electromechanical properties. These nanocomposites are sensitive electromechanical sensors with gauge factors >500 that can measure pulse, blood pressure, and even the impact associated with the footsteps of a small spider.

Liquid exfoliation of solvent-stabilized few-layer black phosphorus for applications beyond electronics.

Few-layer black phosphorus (BP) is a new two-dimensional material which is of great interest for applications, mainly in electronics. However, its lack of environmental stability severely limits its synthesis and processing. Here we demonstrate that high-quality, few-layer BP nanosheets, with controllable size and observable photoluminescence, can be produced in large quantities by liquid phase exfoliation under ambient conditions in solvents such as N-cyclohexyl-2-pyrrolidone (CHP). Nanosheets are surprisingly stable in CHP, probably due to the solvation shell protecting the nanosheets from reacting with water or oxygen. Experiments, supported by simulations, show reactions to occur only at the nanosheet edge, with the rate and extent of the reaction dependent on the water/oxygen content. We demonstrate that liquid-exfoliated BP nanosheets are potentially useful in a range of applications from ultrafast saturable absorbers to gas sensors to fillers for composite reinforcement.

Sensitive, high-strain, high-rate bodily motion sensors based on graphene-rubber composites.

Monitoring of human bodily motion requires wearable sensors that can detect position, velocity and acceleration. They should be cheap, lightweight, mechanically compliant and display reasonable sensitivity at high strains and strain rates. No reported material has simultaneously demonstrated all the above requirements. Here we describe a simple method to infuse liquid-exfoliated graphene into natural rubber to create conducting composites. These materials are excellent strain sensors displaying 10(4)-fold increases in resistance and working at strains exceeding 800%. The sensitivity is reasonably high, with gauge factors of up to 35 observed. More importantly, these sensors can effectively track dynamic strain, working well at vibration frequencies of at least 160 Hz. At 60 Hz, we could monitor strains of at least 6% at strain rates exceeding 6000%/s. We have used these composites as bodily motion sensors, effectively monitoring joint and muscle motion as well and breathing and pulse.

Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids.

To progress from the laboratory to commercial applications, it will be necessary to develop industrially scalable methods to produce large quantities of defect-free graphene. Here we show that high-shear mixing of graphite in suitable stabilizing liquids results in large-scale exfoliation to give dispersions of graphene nanosheets. X-ray photoelectron spectroscopy and Raman spectroscopy show the exfoliated flakes to be unoxidized and free of basal-plane defects. We have developed a simple model that shows exfoliation to occur once the local shear rate exceeds 10(4) s(-1). By fully characterizing the scaling behaviour of the graphene production rate, we show that exfoliation can be achieved in liquid volumes from hundreds of millilitres up to hundreds of litres and beyond. The graphene produced by this method performs well in applications from composites to conductive coatings. This method can be applied to exfoliate BN, MoS2 and a range of other layered crystals.

The role of first formant information in simulated electro-acoustic hearing.

Cochlear implant (CI) recipients with residual hearing show improved performance with the addition of low-frequency acoustic stimulation (electro-acoustic stimulation, EAS). The present study sought to determine whether a synthesized first formant (F1) signal provided benefit to speech recognition in simulated EAS hearing and to compare such benefit with that from other low-frequency signals. A further aim was to determine if F1 amplitude or frequency was more important in determining benefit and if F1 benefit varied with formant bandwidth. In two experiments, sentence recordings from a male speaker were processed via a simulation of a partial insertion CI, and presented to normal hearing listeners in combination with various low-frequency signals, including a tone tracking fundamental frequency (F0), low-pass filtered speech, and signals based on F1 estimation. A simulated EAS benefit was found with F1 signals, and was similar to the benefit from F0 or low-pass filtered speech. The benefit did not differ significantly with the narrowing or widening of the F1 bandwidth. The benefit from low-frequency envelope signals was significantly less than the benefit from any low-frequency signal containing fine frequency information. Results indicate that F1 provides a benefit in simulated EAS hearing but low frequency envelope information is less important than low frequency fine structure in determining such benefit.

Transparent conducting films from NbSe3 nanowires.

We have developed methods to disperse and partially size separate NbSe(3) nanowires in aqueous surfactant solutions. These dispersions can easily be formed into thin films. Optical and electrical studies show these films to display sheet resistances and transmittances ranging from (460 Ω/□, 22%) to (12 kΩ/□, 79%) depending on thickness. For thicker films, we measured the transparent conducting figure of merit to be σ(DC, B)/σ(Op) = 0.32, similar to graphene networks. Thickness measurements gave individual values of σ(Op) = 17,800 S m(-1) and σ(DC, B) = 5700 S m(-1). Films thinner than ∼ 70 nm displayed reduced DC conductivity due to percolative effects.