Ion Co-storage in Porous Organic Frameworks through On-site Coulomb Interactions for High Energy and Power Density Batteries.

Fast and continuous ion insertion is blocked in the common electrodes operating with widely accepted single-ion storage mechanism, primarily due to Coulomb repulsion between the same ions. It results in an irreconcilable conflict between capacity and rate performance. Herein, we designed a porous organic framework with novel multiple-ion co-storage modes, including PF6 - /Li+ , OTF- /Mg2+ , and OTF- /Zn2+ co-storage. The Coulomb interactions between cationic and anionic carriers in the framework can significantly promote electrode kinetics, by rejuvenating fast ion carrier migration toward framework interior. Consequently, the framework via PF6 - /Li+ co-storage mode shows a high energy density of 878 Wh kg-1 cycled more than 20 000 cycles, with an excellent power density of 28 kW kg-1 that is already comparable to commercial supercapacitors. The both greatly improved energy and power densities via the co-storage mode may pave a way for exploring new electrodes that are not available from common single-ion electrodes.

Localized Ligands Assist Ultrafast Multivalent-Cation Intercalation Pseudocapacitance.

Rechargeable batteries based on multivalent cation (Mvn+ , n>1) carriers are considered potentially low-cost alternatives to lithium-ion batteries. However, the high charge-density Mvn+ carriers generally lead to sluggish kinetics and poor structural stability in cathode materials. Herein, we report an Mvn+ storage via intercalation pseudocapacitance mechanism in a 2D bivalve-like organic framework featured with localized ligands. By switching from conventional intercalation to localized ligand-assisted-intercalation pseudocapacitance, the organic cathode exhibits unprecedented fast kinetics with little structural change upon intercalation. It thus enables an excellent power density of 57 kW kg-1 over 20000 cycles for Ca2+ storage and a power density of 14 kW kg-1 with a long cycling life over 45000 cycles for Zn2+ storage. This work may provide a largely unexploited route toward constructing a local dynamic coordination microstructure for ultrafast Mvn+ storage.

Ultrathin Aramid/COF Heterolayered Membrane for Solid-State Li-Metal Batteries.

Ultrathin, ultrastrong, and highly conductive solid-state polymer-based composite electrolytes have long been exploited for the next-generation lithium-based batteries. In particular, the lightweight membranes that are less than tens of microns are strongly desired, aiming to maximize the energy densities of solid-state batteries. However, building such ideal membranes are challenging when using traditional materials and fabrication technologies. Here we reported a 7.1 µm thick heterolayered Kevlar/covalent organic framework (COF) composite membrane fabricated via a bottom-up spin layer-by-layer assembly technology that allows for precise control over the structure and thickness of the obtained membrane. Much stronger chemical/mechanical interactions between cross-linked Kevlar and conductive 2D-COF building blocks were designed, resulting in a highly strong and Li+ conductive (1.62 × 10-4 S cm-1 at 30 °C and 4.6 × 10-4 S cm-1 at 70 °C) electrolyte membrane that can prevent solid-state batteries from short-circuiting after over 500 h of cycling. All-solid-state lithium batteries using this membrane enable a significantly improved energy density.

Broadband noise limit in the photodetection of ultralow jitter optical pulses.

Applications with optical atomic clocks and precision timing often require the transfer of optical frequency references to the electrical domain with extremely high fidelity. Here we examine the impact of photocarrier scattering and distributed absorption on the photocurrent noise of high-speed photodiodes when detecting ultralow jitter optical pulses. Despite its small contribution to the total photocurrent, this excess noise can determine the phase noise and timing jitter of microwave signals generated by detecting ultrashort optical pulses. A Monte Carlo simulation of the photodetection process is used to quantitatively estimate the excess noise. Simulated phase noise on the 10 GHz harmonic of a photodetected pulse train shows good agreement with previous experimental data, leading to the conclusion that the lowest phase noise photonically generated microwave signals are limited by photocarrier scattering well above the quantum limit of the optical pulse train.

Iron-catalyzed benzylic C-H thiolation via photoinduced ligand-to-metal charge-transfer.

Here, we describe an iron-catalyzed benzylic C-H thiolation of alkylarenes via photoinduced ligand-to-metal charge-transfer. The protocol features operational simplicity, mild reaction conditions, and the use of FeCl3 as catalyst and thiols/disulfides as sulfur sources, which enables the transformation of diverse benzylic C-H bonds into C-S bonds with a high efficiency.

Improved sinusoidal gating with balanced InGaAs/InP Single Photon Avalanche Diodes.

We report balanced InGaAs/InP single photon avalanche diodes (SPADs) operated in sinusoidal gating mode with a tunable phase shifter to reduce common mode noise. This technique enables detection of small avalanche pulses, which results in reduced afterpulsing. For laser repletion rate of 20 MHz at 240 K, the dark count rate for photon detection efficiency of 10% is 8.9 kHz.

A semi-fluid multi-functional binder for a high-performance silicon anode of lithium-ion batteries.

Currently, a variety of binders are developed to inhibit the rapid capacity fading of Si. The Si anodes are mainly enhanced by the chemical bonding effect on the surface of conventional solid-state binders. However, with a huge volume change of silicon, solid binders are easily deactivated. Herein, a semi-fluid binder termed GPC is designed based on a viscoelastic crosslinking network with abundant active sites and self-healing performance. The backbone of the binder network is in situ synthesized using guar gum (GG), polyacrylic acid (PAA), and citric acid (CA). Serving as the flexible joints and the plasticizer of the network, CA small molecules remarkably improve the viscoelasticity of the binder to tolerate the volume change of Si via rearranging particles in the network during cycling. Moreover, CA can form a layer of surface coating on Si to stabilize the SEI for long-term electrochemical performance. As a result, the Si@GPC electrode shows excellent cycling stability and exhibits a superb capacity of 1292 mA h g-1 after 1000 cycles at 2 A g-1. This work illustrates the advantages and prospects of designing semi-fluid binders for high-performance batteries.

Robust dual-cross-linked networks enable stable silicon anodes.

The simultaneous attainment of long cycle life and high energy in Si anodes remains challenging. Herein, we introduce the concept of primary building units as organizing units to construct durable and conductive electrode architectures, which helps to facilitate the coalescence of Si nanoparticles with conductive pathways and prevent nanoparticle aggregation.

Nanosphere natural lithography surface texturing as anti-reflective layer on SiC photodiodes.

Natural lithography with 100-nm-diameter SiO(2) spheres followed by inductively coupled plasma etching was used to texture the surface of 4H-SiC for a wide-spectrum large-acceptance-angle anti-reflective layer. The surface showed low normal-incidence reflectance of < 5% over a wide spectrum from 250 nm to 550 nm. Photodiodes fabricated from the surface-textured SiC showed broader spectral and angular responsivity than SiC photodiodes with SiO(2) antireflective coating. The textured SiC photodiodes showed peak responsivity of 116 mA/W, large angle of acceptance angle (< 2% decrease in responsivity at 50° incident angle) and low dark current at 10V.