The status and challenging perspectives of 3D-printed micro-batteries.

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.

Electrochemically Exfoliated Graphene Additive-Free Inks for 3D Printing Customizable Monolithic Integrated Micro-Supercapacitors on a Large Scale.

Three-dimensional (3D) printing technology with enhanced fidelity can achieve multiple functionalities and boost electrochemical performance of customizable planar micro-supercapacitors (MSCs), however, precise structural control of additive-free graphene-based macro-assembly electrode for monolithic integrated MSCs (MIMSCs) remains challenging. Here, the large-scale 3D printing fabrication of customizable planar MIMSCs is reported utilizing additive-free, high-quality electrochemically exfoliated graphene inks, which is not required the conventional cryogenic assistance during the printing process and any post-processing reduction. The resulting MSCs reveal an extremely small engineering footprint of 0.025 cm2, exceptionally high areal capacitance of 4900 mF cm-2, volumetric capacitance of 195.6 F cm-3, areal energy density of 2.1 mWh cm-2, and unprecedented volumetric energy density of 23 mWh cm-3 for a single cell, surpassing most previously reported 3D printed MSCs. The 3D printed MIMSC pack is further demonstrated, with the maximum areal cell count density of 16 cell cm-2, the highest output voltage of 192.5 V and the largest output voltage per unit area of 56 V cm-2 up to date are achieved. This work presents an innovative solution for processing high-performance additive-free graphene ink and realizing the large-scale production of 3D printed MIMSCs for planar energy storage.

Dual-Stimulus-Driven Dynamically Controllable [3]Rotaxane with Tunable Organic Room-Temperature Phosphorescence.

A dual-stimulus-driven stiff-stilbene-based dynamic [3]rotaxane has been facilely developed using the threading-stoppering strategy and exhibits reversible shuttling motions and bidirectional rotations upon encountering acid-base and distinct light stimulations, respectively. Herein, the two dibenzo-24-crown-8 macrocycles can undergo reversible switching motion between two different stations along the axle suffered from acid-base stimulation, and simultaneously, the two rotaxanes can also perform cis-trans rotations upon irradiation with distinct light. In other words, the constructed rotaxanes can conduct two modes of regular motions without interference. Interestingly, reciprocating switching motion of the rings along the axle enabled the rotaxanes to exhibit controllable and reversible photoisomerization speed, conversion yield, and quantum yield. Crucially, these rotaxanes also manifest adjustable solid-state organic room-temperature phosphorescence (RTP) and photoluminescence stimulated by dual factors (acid-base and diverse light), which are further applied in information encryption and anticounterfeiting. The presented study provides an instructive way for precisely boosting photoisomerization performances and the fabrication of dual-stimuli-induced molecular machines with functions of two-mode mechanical motions and controllable pure organic RTP switches.

Multifunctional Mesoporous Polyaniline/Graphene Nanosheets for Flexible Planar Integrated Microsystem of Zinc Ion Microbattery and Gas Sensor.

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.

Achieving stable Na metal cycling via polydopamine/multilayer graphene coating of a polypropylene separator.

Sodium metal batteries are considered one of the most promising low-cost high-energy-density electrochemical energy storage systems. However, the growth of unfavourable Na metal deposition and the limited cell cycle life hamper the application of this battery system at a large scale. Here, we propose the use of polypropylene separator coated with a composite material comprising polydopamine and multilayer graphene to tackle these issues. The oxygen- and nitrogen- containing moieties as well as the nano- and meso- porous network of the coating allow cycling of Na metal electrodes in symmetric cell configuration for over 2000 h with a stable 4 mV overpotential at 1 mA cm-2. When tested in full Na || Na3V2(PO4)3 coin cell, the coated separator enables the delivery of a stable capacity of about 100 mAh g-1 for 500 cycles (90% capacity retention) at a specific current of 235 mA g-1 and satisfactory rate capability performances (i.e., 75 mAh g-1 at 3.5 A g-1).

NH3 Sensor Based on 2D Wormlike Polypyrrole/Graphene Heterostructures for a Self-Powered Integrated System.

The rapid development of a NH3 sensor puts forward a great challenge for active materials and integrated sensing systems. In this work, an ultrasensitive NH3 sensor based on two-dimensional (2D) wormlike mesoporous polypyrrole/reduced graphene oxide (w-mPPy@rGO) heterostructures, synthesized by a universal soft template method is reported, revealing the structure-property coupling effect of the w-mPPy/rGO heterostructure for sensing performance improvement, and demonstrates great potential in the integration of a self-powered sensor system. Remarkably, the 2D w-mPPy@rGO heterostructrure exhibits preferable response toward NH3 (ΔR/R0 = 45% for 10 ppm NH3 with a detection limit of 41 ppb) than those of the spherical mesoporous hybrid (s-mPPy@rGO) and the nonporous hybrid (n-PPy@rGO) due to its large specific surface area (193 m2/g), which guarantees fast gas diffusion and transport of carriers. Moreover, the w-mPPy@rGO heterostructures display outstanding selectivity to common volatile organic compounds (VOCs), H2S, and CO, prominent antihumidity inteference superior to most existing chemosensors, superior reversibility and favorable repeatability, providing high potential for practicability. Thus, a self-powered sensor system composed of a nanogenerator, a lithium-ion battery, and a w-mPPy@rGO-based sensor was fabricated to realize wireless, portable, cost-effective, and light-weight NH3 monitoring. Impressively, our self-powered sensor system exhibits high response toward 5-40 mg NH4NO3, which is a common explosive to generate NH3 via alkaline hydrolysis, rendering it a highly prospective technique in a NH3-based sensing field.

A Two-Dimensional Mesoporous Polypyrrole-Graphene Oxide Heterostructure as a Dual-Functional Ion Redistributor for Dendrite-Free Lithium Metal Anodes.

Guiding the lithium ion (Li-ion) transport for homogeneous, dispersive distribution is crucial for dendrite-free Li anodes with high current density and long-term cyclability, but remains challenging for the unavailable well-designed nanostructures. Herein, we propose a two-dimensional (2D) heterostructure composed of defective graphene oxide (GO) clipped on mesoporous polypyrrole (mPPy) as a dual-functional Li-ion redistributor to regulate the stepwise Li-ion distribution and Li deposition for extremely stable, dendrite-free Li anodes. Owing to the synergy between the Li-ion transport nanochannels of mPPy and the Li-ion nanosieves of defective GO, the 2D mPPy-GO heterostructure achieves ultralong cycling stability (1000 cycles), even tests at 0 and 50 °C, and an ultralow overpotential of 70 mV at a high current density of 10.0 mA cm-2 , outperforming most reported Li anodes. Furthermore, mPPy-GO-Li/LiCoO2 full batteries demonstrate remarkably enhanced performance with a capacity retention of >90 % after 450 cycles. Therefore, this work opens many opportunities for creating 2D heterostructures for high-energy-density Li metal batteries.

Scalable fabrication of printed Zn//MnO2 planar micro-batteries with high volumetric energy density and exceptional safety.

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.

All-Solid-State Planar Sodium-Ion Microcapacitors with Multidirectional Fast Ion Diffusion Pathways.

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.

Ultrahigh Surface Area N-Doped Hierarchically Porous Carbon for Enhanced CO2 Capture and Electrochemical Energy Storage.

Facile synthesis of ultrahigh surface area porous carbons with well-defined functionalities such as N-doping remains a formidable challenge as extensive pore creation results in significant damage to the active sites. Herein, an ultrahigh surface area, N-doped hierarchically porous carbon was prepared through a multicomponent co-assembly approach. The resultant N-doped hierarchically porous carbon (N-HPC) possessed an ultrahigh surface area (≈1960 m2 g-1 ), a uniform interpenetrating micropore (≈1.3 nm) and large mesopore (≈7.6 nm) size, and high N-doping in the carbon frameworks (≈5 wt %). The N-HPC exhibited a high specific capacitance (358 F g-1 at 0.5 A g-1 ) as a supercapacitor electrode in aqueous alkaline electrolyte with a stable cycling performance after10 000 charge/discharge cycles. Moreover, as a CO2 absorbent, N-HPC displayed an adsorption capacity of 29.0 mmol g-1 at 0 °C under a high pressure of 30 bar.

General Interfacial Self-Assembly Engineering for Patterning Two-Dimensional Polymers with Cylindrical Mesopores on Graphene.

Free-standing 2D porous nanomaterials have attracted considerable interest as ideal candidates of 2D film electrodes for planar energy storage devices. Nevertheless, the construction of well-defined mesopore arrays parallel to the lateral surface, which facilitate fast in-plane ionic diffusion, is a challenge. Now, a universal interface self-assembly strategy is used for patterning 2D porous polymers, for example, polypyrrole, polyaniline, and polydopamine, with cylindrical mesopores on graphene nanosheets. The resultant 2D sandwich-structured nanohybrids are employed as the interdigital microelectrodes for the assembly of planar micro-supercapacitors (MSCs), which deliver outstanding volumetric capacitance of 102 F cm-3 and energy density of 2.3 mWh cm-3 , outperforming most reported MSCs. The MSCs display remarkable flexibility and superior integration for boosting output voltage and capacitance.

Electrochemically Scalable Production of Fluorine-Modified Graphene for Flexible and High-Energy Ionogel-Based Microsupercapacitors.

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 ∼93% 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.

All-MXene-Based Integrated Electrode Constructed by Ti3C2 Nanoribbon Framework Host and Nanosheet Interlayer for High-Energy-Density Li-S Batteries.

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.

Graphene-Based Linear Tandem Micro-Supercapacitors with Metal-Free Current Collectors and High-Voltage Output.

Printable supercapacitors are regarded as a promising class of microscale power source, but are facing challenges derived from conventional sandwich-like geometry. Herein, the printable fabrication of new-type planar graphene-based linear tandem micro-supercapacitors (LTMSs) on diverse substrates with symmetric and asymmetric configuration, high-voltage output, tailored capacitance, and outstanding flexibility is demonstrated. The resulting graphene-based LTMSs consisting of 10 micro-supercapacitors (MSs) present efficient high-voltage output of 8.0 V, suggestive of superior uniformity of the entire integrated device. Meanwhile, LTMSs possess remarkable flexibility without obvious capacitance degradation under different bending states. Moreover, areal capacitance of LTMSs can be sufficiently modulated by incorporating polyaniline-based pseudocapacitive nanosheets into graphene electrodes, showing enhanced capacitance of 7.6 mF cm-2 . To further improve the voltage output and energy density, asymmetric LTMSs are fabricated through controlled printing of linear-patterned graphene as negative electrodes and MnO2 nanosheets as positive electrodes. Notably, the asymmetric LTMSs from three serially connected MSs are easily extended to 5.4 V, triple voltage output of the single cell (1.8 V), suggestive of the versatile applicability of this technique. Therefore, this work offers numerous opportunities of graphene and analogous nanosheets for one-step scalable fabrication of flexible tandem energy storage devices integrating with printed electronics on same substrate.

Ti3C2 MXene-Derived Sodium/Potassium Titanate Nanoribbons for High-Performance Sodium/Potassium Ion Batteries with Enhanced Capacities.

Sodium and potassium ion batteries hold promise for next-generation energy storage systems due to their rich abundance and low cost, but are facing great challenges in optimum electrode materials for actual applications. Here, ultrathin nanoribbons of sodium titanate (M-NTO, NaTi1.5O8.3) and potassium titanate (M-KTO, K2Ti4O9) were successfully synthesized by a simultaneous oxidation and alkalization process of Ti3C2 MXene. Benefiting from the suitable interlayer spacing (0.90 nm for M-NTO, 0.93 nm for M-KTO), ultrathin thickness (<11 nm), narrow widths of nanoribbons (<60 nm), and open macroporous structures for enhanced ion insertion/extraction kinetics, the resulting M-NTO exhibited a large reversible capacity of 191 mAh g-1 at 200 mA g-1 for sodium storage, higher than those of pristine Ti3C2 (178 mAh g-1) and commercial TiC derivatives (86 mAh g-1). Notably, M-KTO displayed a superior reversible capacity of 151 mAh g-1 at 50 mA g-1 and 88 mAh g-1 at a high rate of 300 mA g-1 and long-term stable cyclability over 900 times, which outperforms other Ti-based layered materials reported to date. Moreover, this strategy is facile and highly flexible and can be extended for preparing a large number of MXene-derived materials, from the 60+ group of MAX phases, for various applications such as supercapacitors, batteries, and electrocatalysts.

Bottom-Up Fabrication of Sulfur-Doped Graphene Films Derived from Sulfur-Annulated Nanographene for Ultrahigh Volumetric Capacitance Micro-Supercapacitors.

Heteroatom doping of nanocarbon films can efficiently boost the pseudocapacitance of micro-supercapacitors (MSCs); however, wafer-scale fabrication of sulfur-doped graphene films with a tailored thickness and homogeneous doping for MSCs remains a great challenge. Here we demonstrate the bottom-up fabrication of continuous, uniform, and ultrathin sulfur-doped graphene (SG) films, derived from the peripherical trisulfur-annulated hexa-peri-hexabenzocoronene (SHBC), for ultrahigh-rate MSCs (SG-MSCs) with landmark volumetric capacitance. The SG film was prepared by thermal annealing of the spray-coated SHBC-based film, with assistance of a thin Au protecting layer, at 800 °C for 30 min. SHBC with 12 phenylthio groups decorated at the periphery is critical as a precursor for the formation of the continuous and ultrathin SG film, with a uniform thickness of ∼10.0 nm. Notably, the as-produced all-solid-state planar SG-MSCs exhibited a highly stable pseudocapacitive behavior with a volumetric capacitance of ∼582 F cm-3 at 10 mV s-1, excellent rate capability with a remarkable capacitance of 8.1 F cm-3 even at an ultrahigh rate of 2000 V s-1, ultrafast frequency response with a short time constant of 0.26 ms, and ultrahigh power density of ∼1191 W cm-3. It is noteworthy that these values obtained are among the best values for carbon-based MSCs reported to date.

Synthesis, Surface Activities, and Aggregation Behaviors of Butynediol-ethoxylate Modified Polysiloxanes.

Five different butynediol-ethoxylate modified polysiloxanes (PSi-EO) were designed and synthesized via two-step reactions: the preparation of low-hydrogen containing silicone oil (LPMHS) by acid-catalyzed polymerization and the following hydrosilylation reaction with 1,4-bis(2-hydroxyethoxy)-2-butyne. The chemical composition of each product was confirmed by FT-IR, (1)H NMR, and (29)Si NMR. The surface activities and aggregation behaviors of PSi-EO surfactants in aqueous solution were studied systematically using surface tension, dynamic light scattering (DLS), transmission electron microscopy (TEM), and contact-angle methodologies. Relatively low critical aggregation concentration (15-34 mg·L(-1)) and surface tension (∼25 mN·m(-1)) were measured for PSi-EO aqueous solution. The rate of surface tension reduction increased both with increasing PSi-EO concentration and with increases in the proportion of hydrophilic moieties within the synthesized compounds. Furthermore, DLS and TEM studies revealed that PSi-EO self-assembled in aqueous solution to form spherical aggregates. Contact-angle measurements conducted upon low-energy paraffin film surfaces demonstrated that PSi-EO exhibited efficient spreading at concentrations above the critical aggregation concentration.