Robust Zinc Anode Enabled by Sulfonate-Rich MOF-Modified Separator.

Aqueous zinc ion batteries (ZIBs) hold great promise for large-scale energy storage; however, severe zinc dendritic growth and side reactions on the anode dramatically impede their commercial application. Herein, a Zr-based MOF (UiO-66) functionalized with a high density of sulfonic acid (─SO3 H) groups is used to modify the glass fiber (GF) separator of ZIBs, providing a unique solution for stabilizing Zn anode. Benefiting from the strong interaction between zincophilic -SO3 H and Zn2+ , this sulfonate-rich UiO-66 modified GF (GF@UiO-S2) separator not only guarantees the homogeneous distribution of ion flux, but also accelerates the ion migration kinetics. Hence, the GF@UiO-S2 separator promotes uniform Zn plating/stripping on the Zn anode and facilitates the desolvation of hydrated Zn2+ ions at the interface, which helps guide dendrite-free Zn deposition and inhibit undesired side reactions. Accordingly, the Zn||Zn symmetric cell with this separator achieves excellent cycling stability with a long cycle life exceeding 3450 h at 3 mA cm-2 . Besides, the Zn||MnO2 full cell paired with this separator delivers remarkable cyclability with 90% capacity retention after 1200 cycles. This design of metal-organic frameworks functionalized separators provides a new insight for constructing highly robust ZIBs.

Minimalist Design for Solar Energy Conversion: Revamping the π-Grid of an Organic Framework into Open-Shell Superabsorbers.

We apply a versatile reaction to a versatile solid: the former involves the electron-deficient alkene tetracyanoethylene (TCNE) as the guest reactant; the latter consists of stacked 2D honeycomb covalent networks based on the electron-rich ß-ketoenamine hinges that also activate the conjugated, connecting alkyne units. The TCNE/alkyne reaction is a [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) that forms strong push-pull units directly into the backbone of the framework-i.e., using only the minimalist "bare-bones" scaffold, without the need for additional side groups of alkynes or other functions. The ability of the stacked alkyne units (i.e., as part of the honeycomb mass) to undergo such extensive rearrangement highlights the structural flexibility of these covalent organic framework (COF) hosts. The COF solids remain porous, crystalline, and air-/water-stable after the CA-RE modification, while the resulting push-pull units feature distinct open-shell/free-radical character, are strongly light-absorbing, and shift the absorption ends from 590 nm to around 1900 nm (band gaps from 2.17-2.23 to 0.87-0.95 eV), so as to better capture sunlight (especially the infrared region which takes up 52% of the solar energy). As a result, the modified COF materials achieve the highest photothermal conversion performances, holding promise in thermoelectric power generation and solar steam generation (e.g., with solar-vapor conversion efficiencies >96%).

Low-Concentration Redox-Electrolytes for High-Rate and Long-Life Zinc Metal Batteries.

The uncontrolled zinc electrodeposition and side reactions severely limit the power density and lifespan of Zn metal batteries. Herein, the multi-level interface adjustment effect is realized with low-concentration redox-electrolytes (0.2 m KI) additives. The iodide ions adsorbed on the zinc surface significantly suppress water-induced side reactions and by-product formation and enhance the kinetics of zinc deposition. The distribution of relaxation times results reveal that iodide ions can reduce the desolvation energy of hydrated zinc ions and guide the deposition of zinc ions due to their strong nucleophilicity. As a consequence, the Zn||Zn symmetric cell achieves superior cycling stability (>3000 h at 1 mA cm-2 , 1 mAh cm-2 ) accompanied by a uniform deposition and a fast reaction kinetics with a low voltage hysteresis (<30 mV). Additionally, coupled with an activated carbon (AC) cathode, the assembled Zn||AC cell delivers a high-capacity retention of 81.64% after 2000 cycles at 4 A g-1 . More importantly, the operando electrochemical UV-vis spectroscopies show that a small number of I3 - can spontaneously react with the dead zinc as well as basic zinc saltsand regenerate iodide ions and zinc ions; thus, the Coulombic efficiency of each charge-discharge process is close to 100%.

Donor-Acceptor Conjugated Microporous Polymer toward Enhanced Redox Kinetics in Lithium-Sulfur Batteries.

Conjugated microporous polymers (CMPs) with porous structure and rich polar units are favorable for high-performance lithium-sulfur (Li-S) batteries. However, understanding the role of building blocks in polysulfide catalytic conversion is still limited. In this work, two triazine-based CMPs are constructed by electron-accepting triazine with electron-donating triphenylbenzene (CMP-B) or electron-accepting triphenyltriazine (CMP-T), which can grow on a conductive carbon nanotube (CNT) to serve as separator modifiers for Li-S batteries. CMP-B@CNT features faster ion transportation than the counterpart of CMP-T@CNT. More importantly, compared with acceptor-acceptor (A-A) CMP-T, donor-acceptor (D-A) CMP-B possesses a higher degree of conjugation and a narrower band gap, which are conducive to the electron transfer along the polymer skeleton, thus accelerating the sulfur redox kinetics. Consequently, the CMP-B@CNT functional separator endows Li-S cells with an outstanding initial capacity of 1371 mAh g-1 at 0.1 C and favorable cycling stability with a capacity degradation rate of 0.048% per cycle at 1 C for 800 cycles. This work provides insight into the rational design of efficient catalysts for advanced Li-S batteries.

Superprotonic conduction of intrinsically zwitterionic microporous polymers based on easy-to-make squaraine, croconaine and rhodizaine dyes.

Porous organic polymers (POPs) have been prepared via a novel metal free polycondensation between a tritopic indole-based monomer and squaric, croconic and rhodizonic acids. Each of the three POPs exhibited high BET surface areas (331-667 m2 g-1) and zwitterionic structures. Impedance measurements revealed that the intrinsic POPs were relatively weak proton conductors, with a positive correlation between the density of oxo-groups and the proton conduction. Doping the materials with LiCl vastly improved the proton conductivity up to a value of 0.54 S cm-1 at 90 °C and 90% relative humidity.

Thiol-Containing Metal-Organic Framework-Decorated Carbon Cloth as an Integrated Interlayer-Current Collector for Enhanced Li-S Batteries.

Lithium-sulfur (Li-S) batteries hold great promise for new-generation energy storage technologies owing to their overwhelming energy density. However, the poor conductivity of active sulfur and the shuttle effect limit their widespread use. Herein, a carbon cloth decorated with thiol-containing UiO-66 nanoparticles (CC@UiO-66(SH)2) was developed to substitute the traditional interlayer and current collector for Li-S batteries. One side of CC@UiO-66(SH)2 acts as a current collector to load active materials, while the other side serves as an interlayer to further restrain polysulfide shuttling. This two-in-one integrated architecture endows the sulfur cathode with fast electron/ion transport and efficient chemical confinement of polysulfides. More importantly, rich thiol groups in the pores of UiO-66(SH)2 serve to tether polysulfides by both covalent interactions and lithium bonding. Therefore, the Li-S battery equipped with this integrated interlayer-current collector not only delivers an enhanced specific capability (1209 mAh g-1 at 0.1 C) but also exhibits prominent cycling stability (an attenuation rate of 0.037% per cycle for 1000 cycles at 1 C). Meanwhile, the battery achieves a high discharge capacity of 795 mAh g-1 at a sulfur loading of 3.83 mg cm-2. The new metal-organic framework (MOF)-based electrode material reported in this study undoubtedly provides insights into the exploration of functional MOFs for robust Li-S batteries.

Erratum: In Situ Activating Strategy to Significantly Boost Oxygen Electrocatalysis of Commercial Carbon Cloth for Flexible and Rechargeable Zn-Air Batteries.

[This corrects the article DOI: 10.1002/advs.201800760.].

Humidity and Pressure Dual-Responsive Metal-Water Batteries Enabled by Three-In-One All-Polymer Cathodes for Smart Self-Powered Systems.

A conceptually new class of humidity and pressure dual-responsive smart metal-water batteries (SMWBs) is presented, which displays self-tunable energy release and intriguing perceptibility of human respiration and environmental pressure. This battery is enabled by the direct contact of a metal (e.g., Mg or Zn) anode and a well-designed all-polymer dual-sensitive moisture electrode (DSME) made from semiconductive polymer (e.g., polypyrrole)-wrapped 3D macroporous polyurethane sponge, without additional electrolytes and separator. A DSME is cost-effective, easily scalable, compressible, and able to act as a moisture carrier, a hydrogen evolution catalyst, and a pressure and humidity dual-sensitive unit simultaneously. Unique three-in-one integration in the DSME enables favorable modulation of electron/mass transport or redox reactions in the SMWB upon different stimulations. Thus, the assembled SMWB not only delivers good discharge performance with smart energy management but also serves as a reliable self-powered bifunctional responsor for the real-time monitoring of respiration and the perceptibility of pressure. Based on various active metal-polymer pairs (Mg/Zn vs polypyrrole/polyaniline), we also developed a series of dual-responsive batteries, demonstrating a general design idea.

Integrated Photo-Responsive Batteries for Solar Energy Harnessing: Recent Advances, Challenges, and Opportunities.

Invited for this month's cover is the group of Prof. Dingshan Yu from Sun Yat-sen University, China. The Front Cover shows an integrated photo-responsive battery with the simplest two-electrode configuration powering a vehicle under light illumination. The Taiji diagram shows the working principle of this device, which combines photoexcited electrons (e- ) and/or holes (h+ ) with various redox species of the batteries during charging and/or discharging processes to realize the harnessing of solar energy. Read the full text of the Minireview at 10.1002/cplu.201900608.

Versatile, Aqueous Soluble C2N Quantum Dots with Enriched Active Edges and Oxygenated Groups.

C2N has emerged as a new family of promising two-dimensional (2D) layered frameworks in both fundamental studies and potential applications. Transforming bulk C2N into zero-dimensional quantum dots (QDs) could induce unique quantum confinement and edge effects that produce improved or new properties. Despite their appealing potential, C2NQDs remain unexplored, and their intriguing properties and a fundamental understanding of their prominent edge effects are still not well understood. Here, we report the first synthesis of water-soluble C2NQDs via a top-down approach without any foreign stabilizer and exploit their linear/nonlinear optical properties and unique edge-preferential electrocatalytic activity toward polysulfides for versatile applications. The resultant dispersant-free C2NQDs with an average size of less than 5 nm feature rich oxygen-carrying groups and active edges, not only enabling excellent dispersion in water but also creating interesting multifunctionality. They can emit not only blue one-photon luminescence (OPL) under ultraviolet (UV) excitation but also green two-photon luminescence (TPL) with a wide near-infrared (NIR) excitation range of 750-900 nm, enabling their use as a new fluorescent ink. Interestingly, when C2NQDs are introduced to modify commercial separators, they can function as new metal-free catalysts to boost polysulfide redox kinetics and endow Li-S batteries with excellent cycling stability, high rate capability, and large areal capacity (7.0 mA h cm-2) at a high sulfur loading of 8.0 mg cm-2. Detailed theoretical and experimental results indicate that the edge of C2N is more favorable for trapping and catalyzing the polysulfide conversion than the terrace and that the synergy between the active edges and oxygenated groups enriched in C2NQDs remarkably improves polysulfide immobilization and catalytic conversion.

Integrated Photo-Responsive Batteries for Solar Energy Harnessing: Recent Advances, Challenges, and Opportunities.

Photo-responsive batteries that enable the effective combination of solar harvesting and energy conversion/storage functionalities render a potential solution to achieve the large-scale utilization of unlimited and cost-effective solar energy and alleviate the limits of conventional energy storage devices. The internal integration of photo-responsive electrodes into rechargeable batteries with the simplest two-electrode configuration is regarded as a reliable and appealing strategy for highly-efficient and low-cost utilization of solar energy by simplifying the device architecture and improving the energy efficiency. This progress report provides a brief review on photo-responsive batteries with integrated two-electrode configuration that can achieve solar energy conversion/storage in one single device. The basic device architecture, operating principles and practical performance of various photo-responsive systems based on solar energy harvesting in various batteries including Li ion batteries, Li-S batteries, Li-I batteries, dual-liquid redox batteries, Li-O2 batteries, non-Li anode-O2 /air batteries are summarized and discussed. Finally, the future opportunities and challenges regarding the two-electrode photo-responsive batteries are proposed.

Tactile UV- and Solar-Light Multi-Sensing Rechargeable Batteries with Smart Self-Conditioned Charge and Discharge.

A tactile, UV- and solar-light multi-sensing smart rechargeable Zn-air battery (SRZAB) with excellent cell performance, self-conditioned charge/discharge, and reliable environmental responsivity is made by using multi-scale conjugated block-copolymer-carbon nanotube-polyurethane foam assemblies as both a self-standing air electrode and a sensing unit. Multiscale engineering fully exploits the multi-synergy among components to endow the newly designed metal-free multi-sensing air electrode (MSAE) with bifunctional oxygen reduction and evolution activities, pressure sensitivity, and photothermal and photoelectric conversion functions in a single electrode, enabling effective regulation of interface properties, electronic/ionic transport, or redox reactions in SRZAB upon various stimulations and establishing multiple working principles. MSAE-driven SRZAB can be used as compressible power sources, self-powered pressure and optical sensors and light-to-electrochemical energy systems.

In Situ Activating Strategy to Significantly Boost Oxygen Electrocatalysis of Commercial Carbon Cloth for Flexible and Rechargeable Zn-Air Batteries.

An in situ strategy to simultaneously boost oxygen reduction and oxygen evolution (ORR/OER) activities of commercial carbon textiles is reported and the direct use of such ubiquitous raw material as low-cost, efficient, robust, self-supporting, and bifunctional air electrodes in rechargeable Zn-air batteries is demonstrated. This strategy not only furnishes carbon textiles with a large surface area and hierarchical meso-microporosity, but also enables efficient dual-doping of N and S into carbon skeletons while retaining high conductivity and stable monolithic structures. Thus, although original carbon textile has rather poor catalytic activity, the activated textiles without loading other active materials yield effective ORR/OER bifunctionality and stability with a much lower reversible overpotential (0.87 V) than those of Pt/C (1.10 V) and RuO2 (1.02 V) and many reported metal-free bifunctional catalysts. Importantly, they can concurrently function as current collectors and as ORR/OER catalysts for rechargeable aqueous and flexible solid-state Zn-air batteries, showing excellent cell performance, long lifetime, and high flexibility.

Effective Dual Polysulfide Rejection by a Tannic Acid/FeIII Complex-Coated Separator in Lithium-Sulfur Batteries.

The solubility behaviour of polysulfides in electrolyte solutions is a major bottleneck prior to the practical application of the lithium-sulfur battery. To address this issue, we fabricate a tannic acid/FeIII complex-coated polypropylene (PP) separator (TA/FeIII-PP separator) via a simple, fast, and green method. Benefiting from dual-confinement effects based on Lewis acid-base interactions between FeIII and polysulfides as well as the dipole-dipole interactions between rich phenol groups and polysulfides, the migration of polysulfides is effectively suppressed. Meanwhile, the porous structure of the PP separator is not destroyed by an additional coating layer. Thus, the TA/FeIII-PP separator can retain rapid lithium ion transport, eventually leading to a significant improvement in both the discharge capacity and rate performance of the corresponding lithium-sulfur cells. The cell with the TA/FeIII-PP separator presents a low capacity fade of 0.06% per cycle over 1000 cycles at 2.0 C, along with a high Coulombic efficiency of >97% over 300 cycles at 0.5 C. With respect to the one with the bare PP separator, the cell with the TA/FeIII-PP separator exhibits a 1.7-fold increase in the discharge capacity at 3.0 C. The proposed simple and economical approach shows great potential in constructing advanced separators to retard the shuttle effect of polysulfides for lithium-sulfur batteries.