ABSTRACT
Two-dimensional MXenes are key high-capacitance electrode materials for micro-supercapacitors (MSCs) catering to integrated microsystems. However, the narrow electrochemical voltage windows of conventional aqueous electrolytes (≤ 1.23 V) and symmetric MXene MSCs (typically ≤ 0.6 V) substantially limit their output voltage and energy density. Highly concentrated aqueous electrolytes exhibit lower water molecule activity, which inhibits water splitting and consequently widens the operating voltage window. Herein, we report ultrahigh-voltage aqueous planar asymmetric MSCs (AMSCs) based on a highly concentrated LiCl-gel quasi-solid-state electrolyte with MXene (Ti3C2T x ) as the negative electrode and MnO2 nanosheets as the positive electrode (MXene//MnO2-AMSCs). The MXene//MnO2-AMSCs exhibit a high voltage of up to 2.4 V, attaining an ultrahigh volumetric energy density of 53 mWh cm-3. Furthermore, the in-plane geometry and the quasi-solid-state electrolyte enabled excellent mechanical flexibility and performance uniformity in the serially/parallel connected packs of our AMSCs. Notably, the MXene//MnO2-AMSC-based integrated microsystem, in conjunction with solar cells and consumer electronics, could efficiently realize simultaneous energy harvesting, storage, and conversion. The findings of this study provide insights for constructing high-voltage aqueous MXene-based AMSCs as safe and self-sufficient micropower sources in smart integrated microsystems.
ABSTRACT
Transition metal tellurides (TMTs) have been ideal materials for exploring exotic properties in condensed-matter physics, chemistry and materials science1-3. Although TMT nanosheets have been produced by top-down exfoliation, their scale is below the gram level and requires a long processing time, restricting their effective application from laboratory to market4-8. We report the fast and scalable synthesis of a wide variety of MTe2 (M = Nb, Mo, W, Ta, Ti) nanosheets by the solid lithiation of bulk MTe2 within 10 min and their subsequent hydrolysis within seconds. Using NbTe2 as a representative, we produced more than a hundred grams (108 g) of NbTe2 nanosheets with 3.2 nm mean thickness, 6.2 µm mean lateral size and a high yield (>80%). Several interesting quantum phenomena, such as quantum oscillations and giant magnetoresistance, were observed that are generally restricted to highly crystalline MTe2 nanosheets. The TMT nanosheets also perform well as electrocatalysts for lithium-oxygen batteries and electrodes for microsupercapacitors (MSCs). Moreover, this synthesis method is efficient for preparing alloyed telluride, selenide and sulfide nanosheets. Our work opens new opportunities for the universal and scalable synthesis of TMT nanosheets for exploring new quantum phenomena, potential applications and commercialization.
ABSTRACT
Accurately placing very small amounts of electrolyte on tiny micro-supercapacitors (MSCs) arrays in close proximity is a major challenge. This difficulty hinders the development of densely-compact monolithically integrated MSCs (MIMSCs). To overcome this grand challenge, we demonstrate a controllable electrolyte directed assembly strategy for precise isolation of densely-packed MSCs at micron scale, achieving scalable production of MIMSCs with ultrahigh areal number density and output voltage. We fabricate a patterned adhesive surface across MIMSCs, that induce electrolyte directed assembly on 10,000 highly adhesive MSC regions, achieving a 100 µm-scale spatial separation between each electrolyte droplet within seconds. The resultant MIMSCs achieve an areal number density of 210 cells cm-2 and a high areal voltage of 555 V cm-2. Further, cycling the MIMSCs at 190 V over 9000 times manifests no performance degradation. A seamlessly integrated system of ultracompact wirelessly-chargeable MIMSCs is also demonstrated to show its practicality and versatile applicability.
ABSTRACT
In the era of the Internet of Things and wearable electronics, 3D-printed micro-batteries with miniaturization, aesthetic diversity and high aspect ratio, have emerged as a recent innovation that solves the problems of limited design diversity, poor flexibility and low mass loading of materials associated with traditional power sources restricted by the slurry-casting method. Thus, a comprehensive understanding of the rational design of 3D-printed materials, inks, methods, configurations and systems is critical to optimize the electrochemical performance of customizable 3D-printed micro-batteries. In this review, we offer a key overview and systematic discussion on 3D-printed micro-batteries, emphasizing the close relationship between printable materials and printing technology, as well as the reasonable design of inks. Initially, we compare the distinct characteristics of various printing technologies, and subsequently emphatically expound the printable components of micro-batteries and general approaches to prepare printable inks. After that, we focus on the outstanding role played by 3D printing design in the device architecture, battery configuration, performance improvement, and system integration. Finally, the future challenges and perspectives concerning high-performance 3D-printed micro-batteries are adequately highlighted and discussed. This comprehensive discussion aims at providing a blueprint for the design and construction of next-generation 3D-printed micro-batteries.
ABSTRACT
Monolithic integrated micro-supercapacitors (MIMSCs) with high systemic performance and cell-number density are important for miniaturized electronics to empower the Internet of Things. However, fabrication of customizable MIMSCs in an extremely small space remains a huge challenge considering key factors such as materials selection, electrolyte confinement, microfabrication and device-performance uniformity. Here, we develop a universal and large-throughput microfabrication strategy to address all these issues by combining multistep lithographic patterning, spray printing of MXene microelectrodes and controllable 3D printing of gel electrolytes. We achieve the monolithic integration of electrochemically isolated micro-supercapacitors in close proximity by leveraging high-resolution micropatterning techniques for microelectrode deposition and 3D printing for precise electrolyte deposition. Notably, the MIMSCs obtained demonstrate a high areal-number density of 28 cells cm-2 (340 cells on 3.5 × 3.5 cm2), a record areal output voltage of 75.6 V cm-2, an acceptable systemic volumetric energy density of 9.8 mWh cm-3 and an unprecedentedly high capacitance retention of 92% after 4000 cycles at an extremely high output voltage of 162 V. This work paves the way for monolithic integrated and microscopic energy-storage assemblies for powering future microelectronics.
ABSTRACT
Rechargeable sodium-ion microbatteries (NIMBs) constructed using low-cost and abundant raw materials in planar configuration with both cathode and anode on the same substrate hold promise for powering coplanar microelectronics, but are hindered by the low areal capacity owing to the thin microelectrodes. Here, a prototype of planar and flexible 3D-printed NIMBs is demonstrated with 3D interconnected conductive thick microelectrodes for ultrahigh areal capacity and boosted rate capability. Rationally optimized 3D printable inks with appropriate viscosities and high conductivity allow the multilayer printing of NIMB microelectrodes reaching a very high thickness of ≈1200 µm while maintaining effective ion and electron-transfer pathways in them. Consequently, the 3D-printed NIMBs deliver superior areal capacity of 4.5 mAh cm-2 (2 mA cm-2 ), outperforming the state-of-the-art printed microbatteries. The NIMBs show enhanced rate capability with 3.6 mAh cm-2 at 40 mA cm-2 and robust long-term cycle life up to 6000 cycles. Furthermore, the planar NIMB microelectrodes, despite the large thickness, exhibit decent mechanical flexibility under various bending conditions. This work opens a new avenue for the construction of high-performance NIMBs with thick microelectrodes capable of powering flexible microelectronics.
ABSTRACT
MXenes are one of the key materials for micro-supercapacitors (MSCs), integrating miniaturized energy-storage components with microelectronics. However, the energy densities of MSCs are greatly hampered by MXenes' narrow working potential window (typically ≤0.6 V) in aqueous electrolytes. Here, we report the fabrication of high-voltage MXene-MSCs through the efficient regulation of reaction kinetics in 2D Ti3C2T x MXene microelectrodes using a water-in-LiCl (WIL, 20 m LiCl) salt gel electrolyte. Importantly, the intrinsic energy-storage mechanism of MXene microelectrodes in WIL, which is totally different from traditional electrolytes (1 m LiCl), was revealed through in situ and ex situ characterizations. We validated that the suppression of MXene oxidation at high anodic potential occurred due to the high content of WIL regulating anion intercalation in MXene electrodes, which effectively broadened the voltage window of MXene-MSCs. Remarkably, the symmetric planar MXene-MSCs presented a record operating voltage of 1.6 V, resulting in an exceptionally high volumetric energy density of 31.7 mWh cm-3. With the ultra-high ionic conductivity (69.5 mS cm-1) and ultralow freezing point (-57°C) of the WIL gel electrolyte, our MSCs could be operated in a wide temperature range of -40 to 60°C, and worked for a long duration even at -40°C, demonstrative of its practicality in extreme environments.
ABSTRACT
The prosperity of smart portable microdevices urgently requires an advanced integrated microsystem equipped with cost-effective safe microbatteries and ultra-stable sensitive sensors. However, the practical application of smart microdevices is limited by complex active materials with single function. Here, the two-dimensional (2D) mesoporous nanosheets of polyaniline decorated on graphene with large specific surface area of 141 m2 g-1 , ample active sites, comparable conductivity, and ordered mesopores of 18 nm for a new-type co-planar integrated microsystem of zinc ion microbattery and gas sensor are developed. These unique triple-function mesoporous nanosheets are well proved for dendrite-free zinc anode with long cyclability (>500 h) and small overpotential (48 mV), a high performance cathode of zinc ion microbattery with outstanding volumetric capacity of 78 mAh cm-3 outperforming their counterparts reported, and a highly sensitive gas sensor with a resistance response (ΔR/R0 %) of 118% for 20 ppm NH3 . Moreover, the co-planar battery-sensor integrated microsystem exhibits superior mechanical stability and smart integration. Therefore, this work will open many opportunities to develop multifunctional 2D mesoporous materials for high performance smart integrated microsystems.
ABSTRACT
Pursuing high areal energy density and developing scalable fabrication strategies of micro-batteries are the key for the progressive printed microelectronics. Herein, the scalable fabrication of multi-layer printable lithium ion micro-batteries (LIMBs) with ultrahigh areal energy density and exceptional flexibility is reported, based on highly conductive and mechanically stable inks by fully incorporating the polyurethane binders in dibasic esters with high-conducting additives of graphene and carbon nanotubes into active materials to construct a cross-linked conductive network. Benefiting from relatively higher electrical conductivity (≈7000 mS cm-1 ) and stably connected network of microelectrodes, the as-fabricated LIMBs by multi-layer printing display robust areal capacity of 398 µAh cm-2 , and remarkable areal energy density of 695 µWh cm-2 , which are much higher than most LIMBs reported. Further, the printed LIMBs show notable capacity retention of 88% after 3000 cycles, and outstanding flexibility without any structure degradation under various torsion states and folding angles. Importantly, a wearable smart bracelet, composed of a serially connected LIMBs pack, a temperature sensor, and a light-emitting diode, is realized for the automatic detection of body temperature. Therefore, this strategy of fabricating highly conductive and mechanically stable printable ink will open a new avenue for developing high-performance printable LIMBs for smart microelectronics.
Subject(s)
Nanotubes, Carbon , Wearable Electronic Devices , Electronics , Ink , Lithium/chemistry , Nanotubes, Carbon/chemistryABSTRACT
High-quality solid electrolyte is the key to developing high-performance all-solid-state lithium-metal batteries (ASSLMBs). Herein, we report a thin composite polymer electrolyte (CPE) based on nanosized Li6.4La3Zr1.4Ta0.6O12 (N-LLZTO) and the PVDF-HFP matrix through a simple film-casting method. N-LLZTO induces partial dehydrofluorination of the poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix that activates the coordination of Li+ with PVDF-HFP and LLZTO due to Lewis acid-base interactions, which facilitates dissociation of lithium salt to increase the Li+ carrier density. As a result, the as-fabricated composite polymer electrolyte with a 20 wt % N-LLZTO (CPE-20) membrane possesses high ionic conductivity (1.7 × 10-4 S cm-1), a high lithium-ion transference number (0.57), a wide electrochemical window (â¼4.8 V), and good thermal stability. Moreover, the CPE-20 membrane displays excellent electrochemical stability to suppress the lithium dendrite and serves more than 2000 h. The solid-state Li|CPE-20|LiFePO4 pouch cells exhibit excellent cycling and rate performance, as well as high energy density. This study presents an effective strategy to design promising solid-state electrolyte for next-generation ASSLMBs.
ABSTRACT
The future of mankind holds great promise for things like the Internet of Things, personal health monitoring systems, and smart cities. To achieve this ambitious goal, it is imperative for electronics to be wearable, environmentally sustainable, and safe. However, large-scale manufacture of self-sufficient electronic systems by exploiting multifunctional materials still faces significant hurdles. Herein, multitasking aqueous printable MXene inks are reported as an additive-free high-capacitance electrode, sensitive pressure-sensing material, highly conducting current collector, metal-free interconnector, and conductive binder. By directly screen printing MXene inks, MXene-based micro-supercapacitors (MSCs) and lithium-ion microbatteries (LIMBs) are delicately fabricated on various substrates. The as-prepared MSCs exhibit ultrahigh areal capacitance of 1.1 F cm-2 and the serially connected MSCs offer a record voltage of 60 V. The quasi-solid-state LIMBs deliver a robust areal energy density of 154 µWh cm-2 . Furthermore, an all-flexible self-powered integrated system on a single substrate based on the multitasking MXene inks is demonstrated through seamless integration of a tandem solar cell, the LIMB, and an MXene hydrogel pressure sensor. Notably, this integrated system is exceptionally sensitive to body movements with a fast response time of 35 ms. Therefore, this multipurpose MXene ink opens a new avenue for powering future smart appliances.
ABSTRACT
Alkali metals are ideal anodes for high-energy-density rechargeable batteries, while seriously hampered by limited cycle life and low areal capacities. To this end, rationally designed frameworks for dendrite-free and volume-changeless alkali-metal deposition at both high current densities and capacities are urgently required. Herein, a general 3D conductive Ti3C2TX MXene-melamine foam (MXene-MF) is demonstrated as an elastic scaffold for dendrite-free, high-areal-capacity alkali anodes (Li, Na, K). Owing to the lithiophilic nature of F-terminated MXene, conductive macroporous network, and excellent mechanical toughness, the constructed MXene-MF synchronously achieves a high current density of 50 mA cm-2 for Li plating, high areal capacity (50 mAh cm-2) with high Coulombic efficiency (99%), and long lifetime (3800 h), surpassing the Li anodes reported recently. Meanwhile, MXene-MF shows flat voltage profiles for 720 h at 10 mA cm-2 for the Na anode and 800 h at 5 mA cm-2 for the K anode, indicative of the wide applicability. Notably, the high current density of 20 mA cm-2 for 20 mAh cm-2 for the Na anode, accompanying good recyclability was rarely achieved before. When coupled with sulfur or Na3V2(PO4)3 cathodes, the assembled MXene-MF alkali (Li, Na)-based full batteries showcase enhanced rate capability and cycling stability, demonstrating the potential of MXene-MF for advanced alkali-metal batteries.
ABSTRACT
Potassium (K) metal batteries hold great promise as an advanced electrochemical energy storage system because of their high theoretical capacity and cost efficiency. However, the practical application of K metal anodes has been limited by their poor cycling life caused by dendrite growth and large volume changes during the plating/stripping process. Herein, three-dimensional (3D) alkalized Ti3C2 (a-Ti3C2) MXene nanoribbon frameworks were demonstrated as advanced scaffolds for dendrite-free K metal anodes. Benefiting from the 3D interconnected porous structure for sufficient K accommodation, improved surface area for low local current density, preintercalated K in expanded interlayer spacing, and abundant functional groups as potassiophilic nuleation sites for uniform K plating/stripping, the as-formed a-Ti3C2 frameworks successfully suppressed the K dendrites and volume changes at both high capacity and current density. As a result, the a-Ti3C2 based electrodes exhibited an ultrahigh coulombic efficiency of 99.4% at a current density of 3 mA cm-2 with long lifespan up to 300 cycles, and excellent stability for 700 h even at an ultrahigh plating capacity of 10 mA h cm-2. When matched with K2Ti4O9 cathodes, the resulting a-Ti3C2-K//K2Ti4O9 full batteries offered a greatly enhanced rate capacity of 82.9 mA h g-1 at 500 mA g-1 and an excellent cycling stability with high capacity retention (77.7% after 600 cycles) at 200 mA g-1, demonstrative of the great potential of a-Ti3C2 for advanced K-metal batteries.
ABSTRACT
The rapid development of printed and microscale electronics imminently requires compatible micro-batteries (MBs) with high performance, applicable scalability, and exceptional safety, but faces great challenges from the ever-reported stacked geometry. Herein the first printed planar prototype of aqueous-based, high-safety Zn//MnO2 MBs, with outstanding performance, aesthetic diversity, flexibility and modularization, is demonstrated, based on interdigital patterns of Zn ink as anode and MnO2 ink as cathode, with high-conducting graphene ink as a metal-free current collector, fabricated by an industrially scalable screen-printing technique. The planar separator-free Zn//MnO2 MBs, tested in neutral aqueous electrolyte, deliver a high volumetric capacity of 19.3 mAh/cm3 (corresponding to 393 mAh/g) at 7.5 mA/cm3, and notable volumetric energy density of 17.3 mWh/cm3, outperforming lithium thin-film batteries (≤10 mWh/cm3). Furthermore, our Zn//MnO2 MBs present long-term cyclability having a high capacity retention of 83.9% after 1300 cycles at 5 C, which is superior to stacked Zn//MnO2 batteries previously reported. Also, Zn//MnO2 planar MBs exhibit exceptional flexibility without observable capacity decay under serious deformation, and remarkably serial and parallel integration of constructing bipolar cells with high voltage and capacity output. Therefore, low-cost, environmentally benign Zn//MnO2 MBs with in-plane geometry possess huge potential as high-energy, safe, scalable and flexible microscale power sources for direction integration with printed electronics.
ABSTRACT
With the relentless development of smart and miniaturized electronics, the worldwide thirst for microscale electrochemical energy storage devices with form factors is launching a new era of competition. Herein, the first prototype planar sodium-ion microcapacitors (NIMCs) are constructed based on the interdigital microelectrodes of urchin-like sodium titanate as faradaic anode and nanoporous activated graphene as non-faradaic cathode along with high-voltage ionogel electrolyte on a single flexible substrate. By effectively coupling with battery-type anode and capacitor-type cathode, the resultant all-solid-state NIMCs working at 3.5 V exhibit a high volumetric energy density of 37.1 mWh cm-3 and an ultralow self-discharge rate of 44 h from V max to 0.6 V max, both of which surpass most reported hybrid micro-supercapacitors. Through tuning graphene layer covered on the top surface of interdigital microelectrodes, the NIMCs unveil remarkably enhanced power density, owing to the establishment of favorable multidirectional fast ion diffusion pathways that significantly reduce the charge transfer resistance. Meanwhile, the as-fabricated NIMCs present excellent mechanical flexibility without capacitance fade under repeated deformation, and electrochemical stability at a high temperature of 80 °C because of using nonflammable ionogel electrolyte and in-plane geometry. Therefore, these flexible planar NIMCs with multidirectional ion diffusion pathways hold tremendous potential for microelectronics.
ABSTRACT
The rapid development and further modularization of miniaturized and self-powered electronic systems have substantially stimulated the urgent demand for microscale electrochemical energy storage devices, e.g., microbatteries (MBs) and micro-supercapacitors (MSCs). Recently, planar MBs and MSCs, composed of isolated thin-film microelectrodes with extremely short ionic diffusion path and free of separator on a single substrate, have become particularly attractive because they can be directly integrated with microelectronic devices on the same side of one single substrate to act as a standalone microsized power source or complement miniaturized energy-harvesting units. The development of and recent advances in planar MBs and MSCs from the fundamentals and design principle to the fabrication methods of 2D and 3D planar microdevices in both in-plane and stacked geometries are highlighted. Additonally, a comprehensive analysis of the primary aspects that eventually affect the performance metrics of microscale energy storage devices, such as electrode materials, electrolyte, device architecture, and microfabrication techniques are presented. The technical challenges and prospective solutions for high-energy-density planar MBs and MSCs with multifunctionalities are proposed.
ABSTRACT
Scalable production of high-quality heteroatom-modified graphene is critical for microscale supercapacitors but remains a great challenge. Herein, we demonstrate a scalable, single-step electrochemical exfoliation of graphite into highly solution-processable fluorine-modified graphene (FG), achieved in an aqueous fluorine-containing neutral electrolyte, for flexible and high-energy-density ionogel-based microsupercapacitors (FG-MSCs). The electrochemically exfoliated FG nanosheets are characterized by atomic thinness, large lateral size (up to 12 µm), a high yield of >70% with ≤3 layers, and a fluorine doping of 3 at%, allowing for large-scale production of FG-MSCs. Our ionogel-based FG-MSCs deliver high energy density of 56 mWh cm-3, by far outperforming the most reported MSCs. Furthermore, the all-solid-state microdevices offer exceptional cyclability with â¼93% after 5000 cycles, robust mechanical flexibility with 100% of capacitance retention bended at 180°, and outstanding serial and parallel integration without the requirement of metal-based interconnects for high-voltage and high-capacitance output. Therefore, these FG-MSCs represent remarkable potential for electronics.
ABSTRACT
MXene-Ti3C2, as a new class of two-dimensional (2D) transition metal carbides (or nitrides), has been synthesized by exfoliating pristine Ti3AlC2 phases with hydrofluoric acid. The SEM and XRD images show that the resultant MXene possesses a graphene-like 2D nanostructure. and the surface of MXene has been partially terminated with -OH, thus providing a favorable microenvironment for enzyme immobilization and retaining their bioactivity and stability. Considering the unique metallic conductivity, biocompatibility and good dispersion in aqueous phase, the as-prepared MXene was explored as a new matrix to immobilize tyrosinase (a model enzyme) for fabricating a mediator-free biosensor for ultrasensitive and rapid detection of phenol. The varying electrochemical measurements were used to investigate the electrochemical performance of MXene-based tyrosinase biosensors. The results revealed that the direct electron transfer between tyrosinase and electrode could be easily achieved via a surface-controlled electrochemical process. The fabricated MXene-based tyrosinase biosensors exhibited good analytical performance over a wide linear range from 0.05 to 15.5⯵molâ¯L-1, with a low detection limit of 12â¯nmolâ¯L-1 and a sensitivity of 414.4â¯mAâ¯M-1. The proposed biosensing approach also demonstrated good repeatability, reproducibility, long-term stability and high recovery for phenol detection in real water samples. With those excellent performances, MXene with graphene-like structure is proved to be a robust and versatile electrochemical biosensing platform for enzyme-based biosensors and biocatalysis, and has wide potential applications in biomedical detection and environmental analysis.
Subject(s)
Agaricales/enzymology , Biosensing Techniques/methods , Enzymes, Immobilized/chemistry , Monophenol Monooxygenase/chemistry , Nanostructures/chemistry , Phenol/analysis , Titanium/chemistry , Biosensing Techniques/instrumentation , Limit of Detection , Nanostructures/ultrastructureABSTRACT
High-energy-density lithium-sulfur (Li-S) batteries hold promise for next-generation portable electronic devices, but are facing great challenges in rational construction of high-performance flexible electrodes and innovative cell configurations for actual applications. Here we demonstrated an all-MXene-based flexible and integrated sulfur cathode, enabled by three-dimensional alkalized Ti3C2 MXene nanoribbon (a-Ti3C2 MNR) frameworks as a S/polysulfides host (a-Ti3C2-S) and two-dimensional delaminated Ti3C2 MXene (d-Ti3C2) nanosheets as interlayer on a polypropylene (PP) separator, for high-energy and long-cycle Li-S batteries. Notably, an a-Ti3C2 MNR framework with open interconnected macropores and an exposed surface area guarantees high S loading and fast ionic diffusion for prompt lithiation/delithiation kinetics, and the 2D d-Ti3C2 MXene interlayer remarkably prevents the shuttle effect of lithium polysulfides via both chemical absorption and physical blocking. As a result, the integrated a-Ti3C2-S/d-Ti3C2/PP electrode was directly used for Li-S batteries, without the requirement of a metal current collector, and exhibited a high reversible capacity of 1062 mAh g-1 at 0.2 C and enhanced capacity of 632 mAh g-1 after 50 cycles at 0.5 C, outperforming the a-Ti3C2-S/PP electrode (547 mAh g-1) and conventional a-Ti3C2-S on an Al current collector (a-Ti3C2-S/Al) (597 mAh g-1). Furthermore, the all-MXene-based integrated cathode displayed outstanding rate capacity of 288 mAh g-1 at 10 C and long-life cyclability. Therefore, this proposed strategy of constructing an all-MXene-based cathode can be readily extended to assemble a large number of MXene-derived materials, from a group of 60+ MAX phases, for applications such as various batteries and supercapacitors.