Holographic patterning of high-performance on-chip 3D lithium-ion microbatteries.
ABSTRACT: As sensors, wireless communication devices, personal health monitoring systems, and autonomous microelectromechanical systems (MEMS) become distributed and smaller, there is an increasing demand for miniaturized integrated power sources. Although thin-film batteries are well-suited for on-chip integration, their energy and power per unit area are limited. Three-dimensional electrode designs have potential to offer much greater power and energy per unit area; however, efforts to date to realize 3D microbatteries have led to prototypes with solid electrodes (and therefore low power) or mesostructured electrodes not compatible with manufacturing or on-chip integration. Here, we demonstrate an on-chip compatible method to fabricate high energy density (6.5 ?Wh cm(-2)??m(-1)) 3D mesostructured Li-ion microbatteries based on LiMnO2 cathodes, and NiSn anodes that possess supercapacitor-like power (3,600 ?W cm(-2)??m(-1) peak). The mesostructured electrodes are fabricated by combining 3D holographic lithography with conventional photolithography, enabling deterministic control of both the internal electrode mesostructure and the spatial distribution of the electrodes on the substrate. The resultant full cells exhibit impressive performances, for example a conventional light-emitting diode (LED) is driven with a 500-?A peak current (600-C discharge) from a 10-?m-thick microbattery with an area of 4 mm(2) for 200 cycles with only 12% capacity fade. A combined experimental and modeling study where the structural parameters of the battery are modulated illustrates the unique design flexibility enabled by 3D holographic lithography and provides guidance for optimization for a given application.
Project description:Aqueous rechargeable microbatteries are promising on-chip micropower sources for a wide variety of miniaturized electronics. However, their development is plagued by state-of-the-art electrode materials due to low capacity and poor rate capability. Here we show that layered potassium vanadium oxides, K<sub>x</sub>V<sub>2</sub>O<sub>5</sub>·nH<sub>2</sub>O, have an amorphous/crystalline dual-phase nanostructure to show genuine potential as high-performance anode materials of aqueous rechargeable potassium-ion microbatteries. The dual-phase nanostructured K<sub>x</sub>V<sub>2</sub>O<sub>5</sub>·nH<sub>2</sub>O keeps large interlayer spacing while removing secondary-bound interlayer water to create sufficient channels and accommodation sites for hydrated potassium cations. This unique nanostructure facilitates accessibility/transport of guest hydrated potassium cations to significantly improve practical capacity and rate performance of the constituent K<sub>x</sub>V<sub>2</sub>O<sub>5</sub>·nH<sub>2</sub>O. The potassium-ion microbatteries with K<sub>x</sub>V<sub>2</sub>O<sub>5</sub>·nH<sub>2</sub>O anode and K<sub>x</sub>MnO<sub>2</sub>·nH<sub>2</sub>O cathode constructed on interdigital-patterned nanoporous metal current microcollectors exhibit ultrahigh energy density of 103?mWh cm<sup>-3</sup> at electrical power comparable to carbon-based microsupercapacitors.
Project description:The fabrication and spatial positioning of electrodes are becoming central issues in battery technology because of emerging needs for small scale power sources, including those embedded in flexible substrates and textiles. More generally, novel electrode positioning methods could enable the use of nanostructured electrodes and multidimensional architectures in new battery designs having improved electrochemical performance. Here, we demonstrate the synergistic use of biological and nonbiological assembly methods for fabricating and positioning small battery components that may enable high performance microbatteries with complex architectures. A self-assembled layer of virus-templated cobalt oxide nanowires serving as the active anode material in the battery anode was formed on top of microscale islands of polyelectrolyte multilayers serving as the battery electrolyte, and this assembly was stamped onto platinum microband current collectors. The resulting electrode arrays exhibit full electrochemical functionality. This versatile approach for fabricating and positioning electrodes may provide greater flexibility for implementing advanced battery designs such as those with interdigitated microelectrodes or 3D architectures.
Project description:Iron-based polyanionic materials can be exploited to realize low cost, durable, and safe cathodes for both bulk and thin film sodium-ion batteries. Herein, we report pulsed laser deposited mixed phosphate Na4Fe3(PO4)2P2O7 as a positive electrode for thin film sodium-ion microbatteries. The bulk material and thin films of Na4Fe3(PO4)2P2O7 are employed by solution combustion synthesis (SCS) and the pulsed laser deposition (PLD) technique, respectively. Phase purity and the nature of the crystallinity of the thin films were confirmed by grazing incidence X-ray diffraction and transmission electron microscopy. Identification of surface roughness and morphology was obtained from atomic force microscopy and scanning electron microscopy, respectively. Emerging electrochemical properties were observed from charge-discharge profiles of the thin films, which are well comparable to bulk material properties. The Na4Fe3(PO4)2P2O7 thin film electrodes delivered a highly reversible Na+ storage capacity of ?120 mAh g-1 with an excellent stability of over 500 cycles. Electrochemical analysis results revealed that the thickness of the film affects the storage capacity.
Project description:TiO2 nanotube layers (TNTs) decorated with Al2O3/MoS2/Al2O3 are investigated as a negative electrode for 3D Li-ion microbatteries. Homogenous nanosheets decoration of MoS2, sandwiched between Al2O3 coatings within self-supporting TNTs was carried out using atomic layer deposition (ALD) process. The structure, morphology, and electrochemical performance of the Al2O3/MoS2/Al2O3-decorated TNTs were studied using scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and chronopotentiometry. Al2O3/MoS2/Al2O3-decorated TNTs deliver an areal capacity almost three times higher than that obtained for MoS2-decorated TNTs and as-prepared TNTs after 100 cycles at 1C. Moreover, stable and high discharge capacity (414 µAh cm-2) has been obtained after 200 cycles even at very fast kinetics (3C).
Project description:The rapid development of microelectronics has equally rapidly increased the demand for miniaturized energy storage devices. On-chip microsupercapacitors (MSCs), as promising power candidates, possess great potential to complement or replace electrolytic capacitors and microbatteries in various applications. However, the areal capacities and energy densities of the planar MSCs are commonly limited by the low voltage window, the thin layer of the electrode materials and complex fabrication processes. Here, a new-type three-dimensional (3D) tubular asymmetric MSC with small footprint area, high potential window, ultrahigh areal energy density, and long-term cycling stability is fabricated with shapeable materials and photolithographic technologies, which are compatible with modern microelectronic fabrication procedures widely used in industry. Benefiting from the novel architecture, the 3D asymmetric MSC displays an ultrahigh areal capacitance of 88.6 mF cm-2 and areal energy density of 28.69 mW h cm-2, superior to most reported interdigitated MSCs. Furthermore, the 3D tubular MSCs demonstrate remarkable cycling stability and the capacitance retention is up to 91.8% over 12?000 cycles. It is believed that the efficient fabrication methodology can be used to construct various integratable microscale tubular energy storage devices with small footprint area and high performance for miniaturized electronics.
Project description:Three-dimensional (3D) periodic nanostructures underpin a promising research direction on the frontiers of nanoscience and technology to generate advanced materials for exploiting novel photonic crystal (PC) and nanofluidic functionalities. However, formation of uniform and defect-free 3D periodic structures over large areas that can further integrate into multifunctional devices has remained a major challenge. Here, we introduce a laser scanning holographic method for 3D exposure in thick photoresist that combines the unique advantages of large area 3D holographic interference lithography (HIL) with the flexible patterning of laser direct writing to form both micro- and nano-structures in a single exposure step. Phase mask interference patterns accumulated over multiple overlapping scans are shown to stitch seamlessly and form uniform 3D nanostructure with beam size scaled to small 200??m diameter. In this way, laser scanning is presented as a facile means to embed 3D PC structure within microfluidic channels for integration into an optofluidic lab-on-chip, demonstrating a new laser HIL writing approach for creating multi-scale integrated microsystems.
Project description:Long-term stability is one of the most desired functionalities of energy storage microdevices for wearable electronics, wireless sensor networks and the upcoming Internet of Things. Although Li-ion microbatteries have become the dominant energy-storage technology for on-chip electronics, the extension of lifetime of these components remains a fundamental hurdle to overcome. Here, we develop an ultra-stable porous anode based on SnAu alloys able to withstand a high specific capacity exceeding 100 µAh cm-2 at 3?C rate for more than 6000 cycles of charge/discharge. Also, this new anode material exhibits low potential (0.2?V versus lithium) and one of the highest specific capacity ever reported at low C-rates (7.3 mAh cm-2 at 0.1?C). We show that the outstanding cyclability is the result of a combination of many factors, including limited volume expansion, as supported by density functional theory calculations. This finding opens new opportunities in design of long-lasting integrated energy storage for self-powered microsystems.
Project description:An in-house UV lithography setup has been optimized to fabricate low-cost disposable electrochemical sensing Cu electrodes using a copper clad board. In view of the high oxidation probability of copper, the low-cost electrodes were modified using different gold nanostructures and a conducing polymer PEDOT:PSS to attain maximal signal output and improved shelf-life. Zero-dimensional (0D) gold nanoparticles (?40 nm) and three-dimensional (3D) gold nanoflowers (?38 nm) mixed with PEDOT:PSS were used as signal-enhancing conductors for the ultrasensitive detection of our model contaminant, methylene blue dye (MB). The bare copper electrode was sensitive to MB, linearly within the range of 4-100 ?M, with a limit of detection of 3.49 ?M. While for gold nanoparticle-PEDOT:PSS-modified electrode, the sensitivity of the electrode was found to increase linearly in the range of 0.01-0.1 ?M, and for gold nanoflowers-PEDOT:PSS, the sensitivity achieved was 0.01-0.1 ?M with the LOD as 0.0022 ?M. For a PEDOT:PSS-modified Cu electrode, used as a comparative to study the contributing role of gold nanostructures towards improved sensitivity, the linearity was found to be in the range of 0.1-1.9 ?M with the LOD as 0.0228 ?M. A 6 times improvement in signal sensitivity for the nanoflower-PEDOT:PSS electrode compared to the nanoparticle-PEDOT:PSS-modified electrode indicates the influence of nanoparticle shape on the electrode efficiency. 3D gold nanoflowers with a large surface area-to-volume ratio and a high catalytic activity prove to be a superior choice for electrode modification.
Project description:A microfluidic platform for hydrodynamic electrochemical analysis was developed, consisting of a poly(methyl methacrylate) chip and three removable electrodes, each housed in 1/16" OD polyether ether ketone tube which can be removed independently for polishing or replacement. The working electrode was a 100-?m diameter Pt microdisk, located flush with the upper face of a 150 ?m × 20 ?m × 3 cm microchannel, smaller than previously reported for these types of removable electrodes. A commercial leak-less reference electrode was utilized, and a coiled platinum wire was the counter electrode. The platform was evaluated electrochemically by oxidizing a potassium ferrocyanide solution at the working electrode, and a typical limiting current behavior was observed after running linear sweep voltammetry and chronoamperometry, with flow rates 1-6 ?L/min. While microdisk channel electrodes have been simulated before using a finite difference method in an ideal 3D geometry, here we predict the limiting current using finite elements in COMSOL Multiphysics 5.3a, which allowed us to easily explore variations in the microchannel geometry that have not previously been considered in the literature. Experimental and simulated currents showed the same trend but differed by 41% in simulations of the ideal geometry, which improved when channel and electrode imperfections were included.
Project description:An electrochemical sensing chip with an 8 × 8 array of titanium nitride three-dimensional nano-electrodes (TiN 3D-NEA) was designed and fabricated via a standard integrated complementary metal oxide semiconductor process. Each nano-electrode in 3D-NEA exhibited a pole-like structure with a radius of 100 nm and a height of 35 nm. The numeric simulation showed that the nano-electrode with a radius of around 100 nm exhibited a more uniformly distributed electric field and a much higher electric field magnitude compared to that of the microelectrode. Cyclic voltammetry study with Ru(NH₃)₆3+ also revealed that the TiN 3D-NEA exhibited a much higher current density than that obtained from the microelectrode by two orders of magnitude. Further studies showed that the electrocatalytical reduction of hydrogen peroxide (H₂O₂) could occur on a TiN 3D-NEA-based sensing chip with a high sensitivity of 667.2 mA⋅mM-1⋅cm-2. The linear detection range for H₂O₂ was between 0.1 μM and 5 mM with a lowest detection limit of 0.1 μM. These results indicated that the fabricated TiN 3D-NEA exhibited high catalytic activity and sensitivity to H₂O₂ and could be a promising sensor for H₂O₂ measurement.