3D Printed Gallium Battery with Outstanding Energy Storage: Toward Fully Printed Battery-on-the-Board Soft Electronics.

The last decade observed rapid progress in soft electronics. Yet, the ultimate desired goal for many research fields is to fabricate fully integrated soft-matter electronics with sensors, interconnects, and batteries, at the ease of pushing a print button. In this work, an important step is taken toward this by demonstrating an ultra-stretchable thin-film Silver-Gallium (Ag-Ga) battery with an unprecedented combination of areal capacity and mechanical strain tolerance. The Biphasic Gallium-Carbon anode electrode demonstrates a record-breaking areal capacity of 78.7 mAh cm-2, and an exceptional stretchability of 170%, showing clear progress over state-of-the-art. The exceptional theoretical capacity of gallium, along with its natural liquid phase self-healing, and its dendrite-free operation permits excellent electromechanical cycling. All composites of the battery including liquid-metal-based current collectors, and electrodes are sinter-free and digitally printable at room temperature, enabling the use of a wide range of substrates, including heat-sensitive polymer films. Consequently, it is demonstrated for the first time multi-layer, and multi-material digital printing of complex battery-on-the-board stretchable devices that integrate printed sensor, multiple cells of printed battery, highly conductive interconnects, and silicone chips, and demonstrate a tailor-made patch for body-worn electrophysiological monitoring.

Triple crosslinking conductive hydrogels with digitally printable and outstanding mechanical stability for high-resolution conformable bioelectronics.

Soft, conductive, and stretchable hydrogels offer a broad variety of applications, including skin-interfacing electrodes, biomonitoring patches, and electrostimulation. Despite rapid developments over the last decades, a combination of good electrical and mechanical properties, low-cost fabrication, and biocompatibility is yet to be demonstrated. Also, the current methods for deposition and patterning of these hydrogels are manual, and there is a need toward autonomous and digital fabrication techniques. In this work, we demonstrate a novel Gallium (Ga) embedded sodium-alginate-polyacrylamide-LAPONITE® (Ga-SA-PAAM-La) hydrogel, that is ultra-stretchable (Maximum strain tolerance of∼985%), tough (toughness ∼30 kJ m-3), bio-adhesive (adhesion energy ∼216 J m-2), conductive, and digitally printable. Ga nanoparticles are used as radical initiators. By adjusting the sonication parameters, we control the solution viscosity and curing time, thus allowing us to prepare pre-polymers with the desired properties for casting, or digital printing. These hydrogels benefit from a triple-network structure due to the role of Ga droplets as crosslinkers besides BIS (N,N'-methylene-bis-acrylamide) and LAPONITE®, thus resulting in tough composite hydrogels. The inclusion of LAPONITE® into the hydrogel network improved its electrical conductivity, adhesion, digital printability, and its mechanical properties, (>6× compared to the same hydrogel without LAPONITE®). As electrodes in the electrocardiogram, the signal-to-noise ratio was surprisingly higher than the medical-grade Ag/AgCl electrodes, which are applied for monitoring muscles, heart, respiration, and body joint angle through EMG, ECG, and bioimpedance measurements. The results obtained prove that such digitally printed conductive and tough hydrogels can be used as potential electrodes and sensors in practical applications in the next generation of printed wearable computing devices.

Reversible polymer-gel transition for ultra-stretchable chip-integrated circuits through self-soldering and self-coating and self-healing.

Integration of solid-state microchips into soft-matter, and stretchable printed electronics has been the biggest challenge against their scalable fabrication. We introduce, Pol-Gel, a simple technique for self-soldering, self-encapsulation, and self-healing, that allows low cost, scalable, and rapid fabrication of hybrid microchip-integrated ultra-stretchable circuits. After digitally printing the circuit, and placing the microchips, we trigger a Polymer-Gel transition in physically cross-linked block copolymers substrate, and silver liquid metal composite ink, by exposing the circuits to the solvent vapor. Once in the gel state, microchips penetrate to the ink and the substrate (Self-Soldering), and the ink penetrates to the substrate (Self-encapsulation). Maximum strain tolerance of ~1200% for printed stretchable traces, and >500% for chip-integrated soft circuits is achieved, which is 5x higher than the previous works. We demonstrate condensed soft-matter patches and e-textiles with integrated sensors, processors, and wireless communication, and repairing of a fully cut circuits through Pol-Gel.

Bi-Phasic Ag-In-Ga-Embedded Elastomer Inks for Digitally Printed, Ultra-Stretchable, Multi-layer Electronics.

A bi-phasic ternary Ag-In-Ga ink that demonstrates high electrical conductivity, extreme stretchability, and low electromechanical gauge factor (GF) is introduced. Unlike popular liquid metal alloys such as eutectic gallium-indium (EGaIn), this ink is easily printable and nonsmearing and bonds strongly to a variety of substrates. Using this ink and a simple extrusion printer, the ability to perform direct writing of ultrathin, multi-layer circuits that are highly stretchable (max. strain >600%), have excellent conductivity (7.02 × 105 S m-1), and exhibit only a modest GF (0.9) related to the ratio of percent increase in trace resistance with mechanical strain is demonstrated. The ink is synthesized by mixing optimized quantities of EGaIn, Ag microflakes, and styrene-isoprene block copolymers, which functions as a hyperelastic binder. When compared to the same composite without EGaIn, the Ag-In-Ga ink shows over 1 order of magnitude larger conductivity, up to ∼27× lower GF, and ∼5× greater maximum stretchability. No significant change over the resistance of the ink was observed after 1000 strain cycles. Microscopic analysis shows that mixing EGaIn and Ag microflakes promotes the formation of AgIn2 microparticles, resulting in a cohesive bi-phasic ink. The ink can be sintered at room temperature, making it compatible with many heat-sensitive substrates. Additionally, utilizing a simple commercial extrusion based printer, the ability to perform stencil-free, digital printing of multi-layer stretchable circuits over various substrates, including medical wound-dressing adhesives, is demonstrated for the first time.

Untethered Disposable Health Monitoring Electronic Patches with an Integrated Ag2O-Zn Battery, a AgInGa Current Collector, and Hydrogel Electrodes.

Stretchable electronics stickers that adhere to the human skin and collect biopotentials are becoming increasingly popular for biomonitoring applications. Such stickers include electrodes, stretchable interconnects, silicon chips for processing and communication, and batteries. Here, we demonstrate a material architecture and fabrication technique for a multilayer, stretchable, low-cost, rapidly deployable, and disposable sticker that integrates skin-interfacing hydrogel electrodes, stretchable interconnects, and a Ag2O-Zn (silver oxide-zinc) battery. In addition, the application of a printed biphasic current collector (AgInGa) for the Ag2O-Zn battery is reported for the first time. Surprisingly, and unlike previously reported batteries, the battery capacity increases after being subjected to strain cycles and reaches a record-breaking areal capacity of 6.88 mAh cm-2 post stretch. As a proof of concept, an application of heart rate monitoring is presented. The disposable patch is interfaced with a miniature battery-free electronics circuit for data acquisition, processing, and wireless transmission. A version of the patch partially covering the patient's chest can supply enough energy for continuous operation for ∼6 days.

Soft Bioelectronic Stickers: Selection and Evaluation of Skin-Interfacing Electrodes.

Surface biopotentials collected from the human epidermis contain important information about human physiology, such as muscular, heart, and brain activities. However, commercially available wearable biomonitoring devices are generally composed of rigid hardware incompatible with the mechanical compliance of soft human tissues. Thin-film stretchable e-skin circuits that can interface the human skin represent an excellent alternative for long-term wearable biomonitoring. Here, a series of soft and stretchable electrodes are evaluated for their applicability in biopotential sensing. This includes conductive composites made of polydimethylsiloxane (PDMS) as a base substrate and conductive particles, i.e., carbon (cPDMS), silver (AgPDMS), anisotropic z-axis conductors made with silver-coated nickel particles (zPDMS), as well as a combination of a conductive tough hydrogel with PDMS, and finally ultrathin tattoo-like adhesive poly(vinyl alcohol)-coated films with stretchable biphasic Ag-EGaIn electrodes. These electrodes are compared between themselves and against the gold-standard Ag/AgCl and stainless steel electrodes, in order to assess relative performance in signal-to-noise ratio (SNR) during electrocardiography, and electrode-skin impedance for a range of frequencies. Results show a direct relation between conformity of the electrode-skin interface and the SNR value. An all-integrated biomonitoring patch with embedded processing and communication electronics, hydrogel electrodes, and a multilayer liquid metal circuit is presented for electromyography.

Hydroprinted Electronics: Ultrathin Stretchable Ag-In-Ga E-Skin for Bioelectronics and Human-Machine Interaction.

We introduce a soft ultrathin and stretchable electronic skin with surface-mounted components that can be transferred and wrapped around any three-dimensional (3D) surface or self-adhere to the human skin. The ∼5 µm thick circuit is fabricated by printing the pattern over a temporary tattoo paper using a desktop laser printer, which is then coated with a silver ink and eutectic gallium-indium (EGaIn) liquid metal alloy. The resulting "Ag-In-Ga" traces are highly conductive and maintain low electrical resistivity as the circuit is stretched to conform to nondevelopable 3D surfaces. We also address integration of surface-mounted microelectronic chips by introducing a novel z-axis conductive interface composed of magnetically aligned EGaIn-coated Ag-Ni microparticles embedded in polyvinyl alcohol (PVA). This " zPVA conductive glue" allows for robust electrical contacts with microchips that have pins with dimensions as small as 300 µm. If printed on the temporary tattoo transfer paper, the populated circuit can be attached to a 3D surface using hydrographic transfer. Both printing and interfacing processes can be performed at the room temperature. We demonstrate examples of applications, including an electronic tattoo over the human epidermis for electromyography signal acquisition, an interactive circuit with touch buttons, and light-emitting diodes transferred over the 3D printed shell of a robotic prosthetic hand, and a proximity measurement skin transferred over a 3D surface.