Atomic Layer Deposition of Alumina-Coated Thin-Film Cathodes for Lithium Microbatteries.

This work shows the electrochemical performance of sputter-deposited, binder-free lithium cobalt oxide thin films with an alumina coating deposited via atomic layer deposition for use in lithium-metal-based microbatteries. The Al2O3 coating can improve the charge-discharge kinetics and suppress the phase transition that occurs at higher potential limits where the crystalline structure of the lithium cobalt oxide is damaged due to the formation of Co4+, causing irreversible capacity loss. The electrochemical performance of the thin film is analysed by imposing 4.2, 4.4 and 4.5 V upper potential limits, which deliver improved performances for 3 nm of Al2O3, while also highlighting evidence of Al doping. Al2O3-coated lithium cobalt oxide of 3 nm is cycled at 147 µA cm-2 (~2.7 C) to an upper potential limit of 4.4 V with an initial capacity of 132 mAh g-1 (65.7 µAh cm-2 µm-1) and a capacity retention of 87% and 70% at cycle 100 and 400, respectively. This shows the high-rate capability and cycling benefits of a 3 nm Al2O3 coating.

Low Temperature Deposition of Highly Cyclable Porous Prussian Blue Cathode for Lithium-Ion Microbattery.

Small dimension Li-ion microbatteries are of great interest for embedded microsystems and on-chip electronics. However, the deposition of fully crystallized cathode thin film generally requires high temperature synthesis or annealing, incompatible with microfabrication processes of integrated Si devices. In this work, a low temperature deposition process of a porous Prussian blue-based cathode on Si wafers is reported. The active material is electrodeposited under aqueous conditions using a pulsed deposition protocol on a porous dendritic metallic current collector that ensures good electronic conductivity of the composite. The high voltage cathodes exhibit a huge areal capacity of ≈650 µAh cm-2 and are able to withstand more than 2000 cycles at 0.25 mA cm-2 rate. The application of these electrode composites with porous Sn based alloying anodes is also demonstrated for the first time in full cell configuration, with high areal energy of 3.1 J cm-2 and more than 95% reversible capacity. This outstanding performance can be attributed to uniform deposition of Prussian blue materials on conductive matrix, which maintains electronic conductivity while simultaneously providing mechanical integrity to the electrode. This finding opens new horizons in the monolithic integration of energy storage components compatible with the semiconductor industry for self-powered microsystems.

A Durable Ni-Zn Microbattery with Ultrahigh-Rate Capability Enabled by In Situ Reconstructed Nanoporous Nickel with Epitaxial Phase.

Powering device for miniaturized electronics is highly desired with well-maintained capacity and high-rate performance. Though Ni-Zn microbattery can meet the demand to some extent with intrinsic fast kinetic, it still suffers irreversible structure degradation due to the repeated lattice strain. Herein, a stable Ni-Zn microbattery with ultrahigh-rate performance is rationally constructed through in situ electrochemical approaches, including the reconstruction of nanoporous nickel and the introduction of epitaxial Zn(OH)2 nanophase. With the enhanced ionic adsorption effect, the superior reactivity of the superficial nickel-based nanostructure is well stabilized. Based on facile miniaturization and electrochemical techniques, the fabricated nickel microelectrode exhibits 63.8% capacity retention when the current density is 500 times folded, and the modified hydroxides contribute to the great stability of the porous structure (92% capacity retention after 10 000 cycles). Furthermore, when the constructed Ni-Zn microbattery is measured in a practical metric, excellent power density (320.17 mW cm-2 ) and stable fast-charging performance (over 90% capacity retention in 3500 cycles) are obtained. This surface reconstruction strategy for nanostructure provides a new direction for the optimization of electrode structure and enriches high-performance output units for integrated microelectronics.

Regulating Lattice-Water-Adsorbed Ions to Optimize Intercalation Potential in 3D Prussian Blue Based Multi-Ion Microbattery.

Miniaturized energy storage device (MESD) is the core module in microscale electronic equipment, yet its electrochemical performance is far away from the actual requirements. The extensive research efforts have improved the performance of MESD via the fabrication techniques and material construction, while ignoring the expansion of optimization strategy in the combination of energy storage mechanism. Herein, the Prussian blue/Zn microbattery is reported with the regulation of lattice-water-adsorbed intercalated ion. The optimal charge transport of cathode is achieved via the optimization of 3D structure of microelectrode to maximize the electrochemical performance. Also, lattice-water-adsorbed ion storage mechanism is further investigated to guide the design of differential energy storage for cathode and anode. The Cu3 (Fe(CN)6 )2 /Zn microbattery, with K+ inter/deintercalation in the cathode and Zn2+ deplating/plating in the anode, displays high capacity (0.281 mAh cm-2 at 2.5 mA cm-2 ), rate performance (0.181 mAh cm-2 at 25 mA cm-2 ), and cycling stability (77.6% capacity retention after 1500 cycles) enhanced by Cu2+ in the electrolyte. This highly efficient combination of fabrication process, active material, and multi-ion storage for microelectrode shows a high tolerance for optimization strategies, expanding the compatibility of optimization path for high-performance MESD.

Virus-Templated Nickel Phosphide Nanofoams as Additive-Free, Thin-Film Li-Ion Microbattery Anodes.

Transition metal phosphides are a new class of materials generating interest as alternative negative electrodes in lithium-ion batteries. However, metal phosphide syntheses remain underdeveloped in terms of simultaneous control over phase composition and 3D nanostructure. Herein, M13 bacteriophage is employed as a biological scaffold to develop 3D nickel phosphide nanofoams with control over a range of phase compositions and structural elements. Virus-templated Ni5 P4 nanofoams are then integrated as thin-film negative electrodes in lithium-ion microbatteries, demonstrating a discharge capacity of 677 mAh g-1 (677 mAh cm-3 ) and an 80% capacity retention over more than 100 cycles. This strong electrochemical performance is attributed to the virus-templated, nanostructured morphology, which remains electronically conductive throughout cycling, thereby sidestepping the need for conductive additives. When accounting for the mass of additional binder materials, virus-templated Ni5 P4 nanofoams demonstrate the highest practical capacity reported thus far for Ni5 P4 electrodes. Looking forward, this synthesis method is generalizable and can enable precise control over the 3D nanostructure and phase composition in other metal phosphides, such as cobalt and copper.

Advances on Microsized On-Chip Lithium-Ion Batteries.

Development of microsized on-chip batteries plays an important role in the design of modern micro-electromechanical systems, miniaturized biomedical sensors, and many other small-scale electronic devices. This emerging field intimately correlates with the topics of rechargeable batteries, nanomaterials, on-chip microfabrication, etc. In recent years, a number of novel designs are proposed to increase the energy and power densities per footprint area, as well as other electrochemical performances of microsized lithium-ion batteries. These advances may guide the pathway for the future development of microbatteries.

Dual-Graphene Rechargeable Sodium Battery.

Sodium (Na) ion batteries are attracting increasing attention for use in various electrical applications. However, the electrochemical behaviors, particularly the working voltages, of Na ion batteries are substantially lower than those of lithium (Li) ion batteries. Worse, the state-of-the-art Na ion battery cannot meet the demand of miniaturized in modern electronics. Here, we demonstrate that electrochemically exfoliated graphene (EG) nanosheets can reversibly store (PF6- ) anions, yielding high charging and discharging voltages of 4.7 and 4.3 V vs. Na+ /Na, respectively. The dual-graphene rechargeable Na battery fabricated using EG as both the positive and negative electrodes provided the highest operating voltage among all Na ion full cells reported to date, together with a maximum energy density of 250 Wh kg-1 . Notably, the dual-graphene rechargeable Na microbattery exhibited an areal capacity of 35 µAh cm-2 with stable cycling behavior. This study offers an efficient option for the development of novel rechargeable microbatteries with ultra-high operating voltage and high energy density.

Atomic force microscopy studies on molybdenum disulfide flakes as sodium-ion anodes.

A microscale battery comprised of mechanically exfoliated molybdenum disulfide (MoS2) flakes with copper connections and a sodium metal reference was created and investigated as an intercalation model using in situ atomic force microscopy in a dry room environment. While an ethylene carbonate-based electrolyte with a low vapor pressure allowed topographical observations in an open cell configuration, the planar microbattery was used to conduct in situ measurements to understand the structural changes and the concomitant solid electrolyte interphase (SEI) formation at the nanoscale. Topographical observations demonstrated permanent wrinkling behavior of MoS2 electrodes upon sodiation at 0.4 V. SEI formation occurred quickly on both flake edges and planes at voltages before sodium intercalation. Force spectroscopy measurements provided quantitative data on the SEI thickness for MoS2 electrodes in sodium-ion batteries for the first time.

A Photolithographable Electrolyte for Deeply Rechargeable Zn Microbatteries in On-Chip Devices.

Zn batteries show promise for microscale applications due to their compatibility with air fabrication but face challenges like dendrite growth and chemical corrosion, especially at the microscale. Despite previous attempts in electrolyte engineering, achieving successful patterning of electrolyte microscale devices has remained challenging. Here, successful patterning using photolithography is enabled by incorporating caffeine into a UV-crosslinked polyacrylamide hydrogel electrolyte. Caffeine passivates the Zn anode, preventing chemical corrosion, while its coordination with Zn2+ ions forms a Zn2+-conducting complex that transforms into ZnCO3 and 2ZnCO3·3Zn(OH)2 over cycling. The resulting Zn-rich interphase product significantly enhances Zn reversibility. In on-chip microbatteries, the resulting solid-electrolyte interphase allows the Zn||MnO2 full cell to cycle for over 700 cycles with an 80% depth of discharge. Integrating the photolithographable electrolyte into multilayer microfabrication creates a microbattery with a 3D Swiss-roll structure that occupies a footprint of 0.136 mm2. This tiny microbattery retains 75% of its capacity (350 µAh cm-2) for 200 cycles at a remarkable 90% depth of discharge. The findings offer a promising solution for enhancing the performance of Zn microbatteries, particularly for on-chip microscale devices, and have significant implications for the advancement of autonomous microscale devices.

Vertical Graphene Film Enables High-Performance Quasi-Solid-State Planar Zinc-Ion Microbatteries.

With the advantages of low cost, high safety, and environmental friendliness, quasi-solid-state zinc-ion microbatteries (ZIMBs) have received widespread attention in the field of flexible wearable devices and on-chip integratable energy storage. However, hysteresis Zn-ion transport kinetics and inhomogeneous growth of the zinc anode result in the poor capacity reversibility and cycling stability. Herein, a quasi-solid-state planar zinc-ion cell was developed by employing a vertical graphene (VG) film as an effective conductive modification layer for both the cathode and anode. The VG distinctly induces uniform Zn deposition/stripping, accelerates the charge transport, and enhances the adhesion between the active materials and current collectors. As a result, planar Zn@VG//MnO2@VG exhibits a high areal capacity of 159 µAh cm-2, a remarkably high areal energy/power density of 201.5 µWh cm-2/67.16 µW cm-2, and a high capacity retention of 95.6% at a bending angle of 180°. The proposed facile strategy for electrode modification provides a new insight into the design of high-performance flexible and planar ZIMBs.

Alkaline Ni-Zn Microbattery Based on 3D Hierarchical Porous Ni Microcathode with High-Rate Performance.

Miniaturized energy storage devices with superior performance and compatibility with facile fabrication are highly desired in smart microelectronics. Typical fabrication techniques are generally based on powder printing or active material deposition, which restrict the reaction rate due to the limited optimization of electron transport. Herein, we proposed a new strategy for the construction of high-rate Ni-Zn microbatteries based on a 3D hierarchical porous nickel (Ni) microcathode. With sufficient reaction sites from the hierarchical porous structure as well as excellent electrical conductivity from the superficial Ni-based activated layer, this Ni-based microcathode is featured with fast-reaction capability. By virtue of facile electrochemical treatment, the fabricated microcathode realized an excellent rate performance (over 90% capacity retention when the current density increased from 1 to 20 mA cm-2). Furthermore, the assembled Ni-Zn microbattery achieved a rate current of up to 40 mA cm-2 with a capacity retention of 76.9%. Additionally, the high reactivity of the Ni-Zn microbattery is also durable in 2000 cycles. This 3D hierarchical porous Ni microcathode, as well as the activation strategy, provides a facile route for the construction of microcathodes and enriches high-performance output units for integrated microelectronics.

All-Printed 3D Solid-State Rechargeable Zinc-Air Microbatteries.

Lightweight, compact, integrated, and miniaturized energy devices are under high pursuit for portable and wearable electronics. However, improving the energy density per area still remains a long-standing challenge. Herein, we report the design and fabrication of a solid-state zinc-air microbattery (ZAmB) by a facile 3D direct printing technique. The interdigital electrodes, gel electrolyte, and encapsulation frame are all printed with a customized design by optimzing the composition of the printing inks to obtain the best battery performance. Multiple layers of interdigital electrodes are sequentially printed with a fine overlap to achieve an ultrahigh thickness of 2.5 mm for a remarkably increased specific areal energy of up to 77.2 mWh cm-2. To meet the practical powering requirements for different output voltages and currents, battery modules consisting of individual ZAmBs connected in series or parallel or a combination of the two are printed with a facile integration to external loads. Powering of LEDs, digital watch, and a miniature rotary motor and even charging of a smartphone by the printed ZAmB modules are successfully demonstrated. The versatile 3D direct printing technique enables the fabricated ZAmBs with an adjustable form factor and integration capability with other electronics, paving the way for exploring new energy systems with diverse structures and extended functionalities.

Annealing Optimization of Lithium Cobalt Oxide Thin Film for Use as a Cathode in Lithium-Ion Microbatteries.

The microbatteries field is an important direction of energy storage systems, requiring the careful miniaturization of existing materials while maintaining their properties. Over recent decades, LiCoO2 has attracted considerable attention as cathode materials for lithium-ion batteries due to its promising electrochemical properties for high-performance batteries. In this work, the thin films of LiCoO2 were obtained by radio-frequency magnetron sputtering of the corresponding target. In order to obtain the desired crystal structure, the parameters such as annealing time, temperature, and heating rate were varied and found to influence the rhombohedral phase formation. The electrochemical performances of the prepared thin films were examined as a function of annealing time, temperature, and heating rate. The LiCoO2 thin film cathode annealed at 550 °C for 1 h 20 min demonstrated the best cycling performance with a discharge specific capacity of around 135 mAh g-1 and volumetric capacity of 50 µAh cm-2µm-1 with a 77% retention at 0.5 C rate.

Fabrication of Single-Particle Microelectrodes and Their Electrochemical Properties.

Compared with traditional centimeter-level electrodes, microelectrodes exhibit a small reaction area, high sensitivity, fast mass transfer rate, and low polarization current. However, current microelectrode preparation processes are very complicated and costly. Herein, we proposed a facile and universal method for fabricating single-particle microelectrodes. In the precursor solution, polyvinyl alcohol and ammonia were introduced as the polymeric binder and pore-forming agent, respectively. Through spaying-drying-sintering processes, the single-particle microelectrodes were successfully prepared for Li4Ti5O12 (LTO), LiCrTiO4 (LCTO), and LiFePO4/C (LFP/C), which showed excellent electrochemical properties. Furthermore, the single-particle microelectrode can be adopted to study the electrochemical oscillations of Li-ion batteries and assemble a full-cell microbattery as a potential next-generation microscale power source.

Sputtered LiCoO2 Cathode Materials for All-solid-state Thin-film Lithium Microbatteries.

This review article presents the literature survey on radio frequency (RF)-magnetron sputtered LiCoO2 thin films used as cathode materials in all-solid-state rechargeable lithium microbatteries. As the process parameters lead to a variety of texture and preferential orientation, the influence of the sputtering conditions on the deposition of LiCoO2 thin films are considered. The electrochemical performance is examined as a function of composition of the sputter Ar/O2 gas mixture, gas flow rate, pressure, nature of substrate, substrate temperature, deposition rate, and annealing temperature. The state-of-the-art of lithium microbatteries fabricated by the rf-sputtering method is also reported.

Facile Development Strategy of a Single Carbon-Fiber-Based All-Solid-State Flexible Lithium-Ion Battery for Wearable Electronics.

Microsized and shape-versatile flexible and wearable lithium-ion batteries (LIBs) are promising and smart energy storage devices for next-generation electronics. In the present work, we design and fabricate the first prototype of microsized fibrous LIBs (thickness ≈ 22 µm) based on multilayered coaxial structure of solid-state battery components over flexible and electrically conductive carbon fibers (CFs). The micro coaxial batteries over the CF surface were fabricated via electrophoretic deposition and dip-coating methods. The microfiber battery showed a stable potential window of 2.5 V with an areal discharge capacity of ∼4.2 µA h cm-2 at 13 µA cm-2 of the current density. The as-assembled battery fiber delivered a comparable energy density (∼0.006 W h cm-3) with solid-state lithium thin-film batteries at higher power densities (∼0.0312 W cm-3). The fibrous batteries were also connected in parallel and in series to deliver large current and high voltage, respectively. The fibrous battery also retains up to 85% discharge capacity even after 100 charge-discharge cycles. Furthermore, these battery fibers performed well under both static and bending conditions, which shows the robustness of the battery fiber. Therefore, this type of fibrous microbattery can be used in advanced flexible and wearable microelectronics, bioelectronics, robotics, and textile applications.

Copolymer Solid-State Electrolytes for 3D Microbatteries via Initiated Chemical Vapor Deposition.

Reliable integration of thin film solid-state polymer electrolytes (SPEs) with 3D electrodes is one major challenge in microbattery fabrication. We used initiated chemical vapor deposition (iCVD) to produce a series of nanoscale copolymer films comprising hydroxyethyl methacrylate and ethylene glycol diacrylate. Conformal copolymer coatings were applied to a variety of patterned 3D electrodes and subsequently converted into ionic conductors by lithium salt doping. Broad tunability in ionic conductivity was achieved by optimizing the copolymer cross-linking density and matrix polarity, resulting in a room-temperature conductivity of (6.1 ± 2.7) × 10-6 S cm-1, the highest value reported for conformal, nanoscale SPEs.

In Situ Formation of WO3-Based Heterojunction Photoanodes with Abundant Oxygen Vacancies via a Novel Microbattery Method.

Non-stoichiometric ratio semiconductor materials have exhibited excellent performance in energy conversion and storage fields. However, the hydrogen treatment method that is commonly used to introduce oxygen vacancies is expensive and dangerous. In this paper, a novel microbattery method using Zn powder and Fe powder as reductant has been developed to synthesize the oxygen vacancy modified WO3- x films and oxygen-deficient heterojunction films (ZnWO4- x/WO3- x and Fe2O3- x/WO3- x) at room temperature. The as-prepared WO3- x and ZnWO4- x/WO3- x heterojunction films exhibit improved photoelectrochemical performance. It is worth noting that this microbattery method can quickly introduce oxygen vacancies into semiconductor materials, including powders and films at room temperature.

Toward Solid-State 3D-Microbatteries Using Functionalized Polycarbonate-Based Polymer Electrolytes.

3D microbatteries (3D-MBs) impose new demands for the selection, fabrication, and compatibility of the different battery components. Herein, solid polymer electrolytes (SPEs) based on poly(trimethylene carbonate) (PTMC) have been implemented in 3D-MB systems. 3D electrodes of two different architectures, LiFePO4-coated carbon foams and Cu2O-coated Cu nanopillars, have been coated with SPEs and used in Li cells. Functionalized PTMC with hydroxyl end groups was found to enable uniform and well-covering coatings on LiFePO4-coated carbon foams, which was difficult to achieve for nonfunctionalized polymers, but the cell cycling performance was limited. By employing a SPE prepared from a copolymer of TMC and caprolactone (CL), with higher ionic conductivity, Li cells composed of Cu2O-coated Cu nanopillars were constructed and tested both at ambient temperature and 60 °C. The footprint areal capacity of the cells was ca. 0.02 mAh cm-2 for an area gain factor (AF) of 2.5, and 0.2 mAh cm-2 for a relatively dense nanopillar-array (AF = 25) at a current density of 0.008 mA cm-2 under ambient temperature (22 ± 1 °C). These results provide new routes toward the realization of all-solid-state 3D-MBs.

Biocompatible Symmetric Na-Ion Microbatteries with Sphere-in-Network Heteronanomat Electrodes Realizing High Reliability and High Energy Density for Implantable Bioelectronics.

The prolonged life expectancy accelerates the development of implantable bioelectronic devices. However, conventional batteries with limited lifetime, rigid architecture, and inferior energy density greatly restrict their applications in patient's body. Herein, a novel flexible symmetric Na-ion microbattery based on the heteronanomat electrode and the biocompatible electrolyte has been developed. The film electrodes with sphere-in-network architecture are synthesized by simultaneously electrospinning and electrospraying followed by carbonization. The combined technologies allow a uniform incorporation of active materials/C spheres into the carbon nanofiber matrix, which results in the heteronanomat electrodes with robust structure, fast electron/ion transport, and compact mass loading. The flexible microbatteries are fabricated based on the interdigitated microelectrodes and the biocompatible electrolytes, which provides a new implantable power source for bioelectronics. As a proof-of-concept study, the symmetric sodium-ion microbatteries are constructed from the heteronanomat bifunctional electrodes (based on Na2VTi(PO4)3) and the biocompatible electrolyte. The high reversibility, fast kinetics, and high energy density of the symmetric system in the biocompatible electrolytes reveal their superior performance in bioenvironments. Moreover, the high capacity retention (over 98%) and the high stability of microbattery implanted in a living SD rat for a month further demonstrate its high reliability for long-term in vivo diagnosis. Therefore, this work not only presents a new sphere-in-net heteronanomat structure for fabricating high-performance electrode but also gives significant contributions to develop high-energy-density and high safety biocompatible power sources of implantable bioelectronics.