Hybrid ion/electron interfacial regulation stabilizes the cobalt/oxygen redox of ultrahigh-voltage lithium cobalt oxide for fast-charging cyclability.

High-voltage and fast-charging LiCoO2 (LCO) is key to high-energy/power-density Li-ion batteries. However, unstable surface structure and unfavorable electronic/ionic conductivity severely hinder its high-voltage fast-charging cyclability. Here, we construct a Li/Na-B-Mg-Si-O-F-rich mixed ion/electron interface network on the 4.65 V LCO electrode to enhance its rate capability and long-term cycling stability. Specifically, the resulting artificial hybrid conductive network enhances the reversible conversion of Co3+/4+/O2-/n- redox by the interfacial ion-electron cooperation and suppresses interface side reactions, inducing an ultrathin yet compact cathode electrolyte interphase. Simultaneously, the derived near-surface Na+/Mg2+/Si4+-pillared local intercalation structure greatly promotes the Li+ diffusion around the 4.55 V phase transition and stabilizes the cathode interface. Finally, excellent 3 C (1 C = 274 mA g-1) fast charging performance is demonstrated with 73.8% capacity retention over 1000 cycles. Our findings shed new insights to the fundamental mechanism of interfacial ion/electron synergy in stabilizing and enhancing fast-charging cathode materials.

Monolithically integrated micro-supercapacitors with high areal number density produced by surface adhesive-directed electrolyte assembly.

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.

Metal telluride nanosheets by scalable solid lithiation and exfoliation.

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.

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.

Breaking the Ru-O-Ru Symmetry of a RuO2 Catalyst for Sustainable Acidic Water Oxidation.

Proton exchange membrane water electrolysis is a highly promising hydrogen production technique for sustainable energy supply, however, achieving a highly active and durable catalyst for acidic water oxidation still remains a formidable challenge. Herein, we propose a local microenvironment regulation strategy for precisely tuning In-RuO2 /graphene (In-RuO2 /G) catalyst with intrinsic electrochemical activity and stability to boost acidic water oxidation. The In-RuO2 /G displays robust acid oxygen evolution reaction performance with a mass activity of 671 A gcat -1 at 1.5 V, an overpotential of 187 mV at 10 mA cm-2 , and long-lasting stability of 350 h at 100 mA cm-2 , which arises from the asymmetric Ru-O-In local structure interactions. Further, it is unraveled theoretically that the asymmetric Ru-O-In structure breaks the thermodynamic activity limit of the traditional adsorption evolution mechanism which significantly weakens the formation energy barrier of OOH*, thus inducing a new rate-determining step of OH* absorption. Therefore, this strategy showcases the immense potential for constructing high-performance acidic catalysts for water electrolyzers.

Aqueous Organic Batteries Using the Proton as a Charge Carrier.

Benefiting from the merits of low cost, nonflammability, and high operational safety, aqueous rechargeable batteries have emerged as promising candidates for large-scale energy-storage applications. Among various metal-ion/non-metallic charge carriers, the proton (H+ ) as a charge carrier possesses numerous unique properties such as fast proton diffusion dynamics, a low molar mass, and a small hydrated ion radius, which endow aqueous proton batteries (APBs) with a salient rate capability, a long-term life span, and an excellent low-temperature electrochemical performance. In addition, redox-active organic molecules, with the advantages of structural diversity, rich proton-storage sites, and abundant resources, are considered attractive electrode materials for APBs. However, the charge-storage and transport mechanisms of organic electrodes in APBs are still in their infancy. Therefore, finding suitable electrode materials and uncovering the H+ -storage mechanisms are significant for the application of organic materials in APBs. Herein, the latest research progress on organic materials, such as small molecules and polymers for APBs, is reviewed. Furthermore, a comprehensive summary and evaluation of APBs employing organic electrodes as anode and/or cathode is provided, especially regarding their low-temperature and high-power performances, along with systematic discussions for guiding the rational design and the construction of APBs based on organic electrodes.

Monolithic integrated micro-supercapacitors with ultra-high systemic volumetric performance and areal output voltage.

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.

A Thermoregulatory Flexible Phase Change Nonwoven for All-Season High-Efficiency Wearable Thermal Management.

Phase change materials have a key role for wearable thermal management, but suffer from poor water vapor permeability, low enthalpy value and weak shape stability caused by liquid phase leakage and intrinsic rigidity of solid-liquid phase change materials. Herein, we report for the first time a versatile strategy for designed assembly of high-enthalpy flexible phase change nonwovens (GB-PCN) by wet-spinning hybrid graphene-boron nitride (GB) fiber and subsequent impregnating paraffins (e.g., eicosane, octadecane). As a result, our GB-PCN exhibited an unprecedented enthalpy value of 206.0 J g-1, excellent thermal reliability and anti-leakage capacity, superb thermal cycling ability of 97.6% after 1000 cycles, and ultrahigh water vapor permeability (close to the cotton), outperforming the reported PCM films and fibers to date. Notably, the wearable thermal management systems based on GB-PCN for both clothing and face mask were demonstrated, which can maintain the human body at a comfortable temperature range for a significantly long time. Therefore, our results demonstrate huge potential of GB-PCN for human-wearable passive thermal management in real scenarios.

High-Voltage MXene-Based Supercapacitors: Present Status and Future Perspectives.

As an emerging class of 2D materials, MXene exhibits broad prospects in the field of supercapacitors (SCs). However, the working voltage of MXene-based SCs is relatively limited (typically ≤ 0.6 V) due to the oxidation of MXene electrode and the decomposition of electrolyte, ultimately leading to low energy density of the device. To solve this issue, high-voltage MXene-based electrodes and corresponding matchable electrolytes are developed urgently to extend the voltage window of MXene-based SCs. Herein, a comprehensive overview and systematic discussion regarding the effects of electrolytes (aqueous, organic, and ionic liquid electrolytes), asymmetric device configuration, and material modification on the operating voltage of MXene-based SCs, is presented. A deep dive is taken into the latest advances in electrolyte design, structure regulation, and high-voltage mechanism of MXene-based SCs. Last, the future perspectives on high-voltage MXene-based SCs and their possible development directions are outlined and discussed in depth, providing new insights for the rational design and realization of advanced next-generation MXene-based electrodes and high-voltage electrolytes.

Kinetic regulation of MXene with water-in-LiCl electrolyte for high-voltage micro-supercapacitors.

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.

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.

Multi-Layer Printable Lithium Ion Micro-Batteries with Remarkable Areal Energy Density and Flexibility for Wearable Smart Electronics.

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.

Multitasking MXene Inks Enable High-Performance Printable Microelectrochemical Energy Storage Devices for All-Flexible Self-Powered Integrated Systems.

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.

The Road Towards Planar Microbatteries and Micro-Supercapacitors: From 2D to 3D Device Geometries.

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.