Catalytically Induced Robust Inorganic-Rich Cathode Electrolyte Interphase for 4.5 V Li||NCM622 Batteries

Tailoring inorganic components of cathode electrolyte interphase (CEI) and solid electrolyte interphase (SEI) is critical to improving the cycling performance of lithium metal batteries. However, it is challenging due to complicated electrolyte reactions on cathode/anode surfaces. Herein, the species and inorganic component content of the CEI/SEI is enriched with an objectively gradient distribution through employing pentafluorophenyl 4-nitrobenzenesulfonate (PFBNBS) as electrolyte additive guided by engineering bond order with functional groups. In addition, a catalytic effect of LiNi_0.6Mn_0.2Co_0.2O₂ (NCM622) cathode is proposed on the decomposition of PFBNBS. PFBNBS with lower highest occupied molecular orbital can be preferentially oxidized on the NCM622 surface with the help of the catalytic effect to induce an inorganic-rich CEI for superior electrochemical performance at high voltage. Moreover, PFBNBS can be reduced on the Li surface due to its lower lowest unoccupied molecular orbital , increasing inorganic moieties in SEI for inhibiting Li dendrite generation. Thus, 4.5 V Li||NCM622 batteries with such electrolyte can retain 70.4% of initial capacity after 500 cycles at 0.2 C, which is attributed to the protective effect of the excellent CEI on NCM622 and the inhibitory effect of its derived CEI/SEI on continuous electrolyte decomposition.     

Self-Mineralizing Dnazyme Hydrogel as a Multifaceted Bone Microenvironment Amendment for Promoting Osteogenesis in Osteoporosis

The accumulation of reactive oxygen species (ROS) and minimal osteogenic raw material in the osteoporotic bone microenvironment greatly inhibits the activity of osteoblasts. Herein, it is originally proposed to construct a biomatrix multifaceted bone microenvironment amendment -Mineralized zippered G4-Hemin DNAzyme hydrogel (MDH)-to improve osteoporotic osteogenic capacity and promote high-quality bone defect repair. The programmed design of the rolling circle amplified DNA hydrogel synthesis system allows the introduction of massive amounts of zippered G4-Hemin DNAzyme in MDH. The zippered G4-Hemin DNAzyme highly mimics the tight catalytic configuration of horseradish peroxidase and exerts excellent enzyme-like activity with considerable ROS molecule scavenging ability. In addition, the DNA amplification by-product pyrophosphate is ingeniously employed as a sufficient phosphorus source, thus constituting an autonomous mineralization system for waste reuse through the introduction of pyrophosphate hydrolase and calcium ions, which deposits in MDH as an osteogenic raw material and addresses the challenge of DNA hydrogel bio-application stability. The remarkable in vitro and in vivo outcomes demonstrate that MDH can effectively improve the oxidative stress status of osteoblasts, restore the balance of mitochondrial membrane potential, and reduce apoptosis, ultimately demonstrating superior osteogenic capacity.     

Ultra-Thin Single-Particle-Layer Sodium Beta-Alumina-Based Composite Polymer Electrolyte Membrane for Sodium-Metal Batteries

Inorganic/organic composite polymer electrolytes (CPEs) with good flexibility and electrode contact have been pursued for solid−state sodium-metal batteries. However, the application of CPEs for high energy density solid−state sodium-metal batteries is still limited by the low Na⁺ conductivity, large thickness, and low ion transference number. Herein, an ultra-thin single-particle-layer (UTSPL) composite polymer electrolyte membrane with a thickness of ≈20 µm straddled by a sodium beta−alumina ceramic electrolyte (SBACE) is presented. A ceramic Na⁺-ion electrolyte that bridges or percolates across an ultra-thin and flexible polymer membrane provides: 1) the strength and flexibility from the polymer membrane, 2) excellent electrolyte/electrode interfacial contact, and 3) a percolation path for Na⁺-ion transfer. Owing to this novel design, the obtained UTSPL-35SBACE membrane exhibits a high Na⁺-ion conductivity of 0.19 mS cm⁻¹ and a transference number of 0.91 at room temperature, contributing to long−term cycling stability of symmetric sodium cells with a small overpotential. The assembled quasi-solid-state cell with the as−prepared UTSPL-35SBACE membrane displays superior cycling performance with a discharge capacity of 105 mAh g⁻¹ at 0.5 °C rate after 100 cycles and excellent rate performance (82 mAh g⁻¹ at 5 °C rate) at room temperature with the potassium manganese hexacyanoferrate (KMHCF)@CNTs/CNFs cathode, where KMHCF refers to potassium manganese hexacyanoferrate.     

Cell Development Enhanced Bionic Silk Hydrogel on Remodeling Immune Pathogenesis of Spinal Cord Injury via M2 Polarization of Microglial

Due to the complex spatial-temporal pathophysiology of spinal cord injury (SCI), effective modulation of SCI-specific inflammatory pathogenesis to achieve desirable therapeutic effects on functional recovery still remains challenging. Herein, cell-enhanced photocrosslinked silk fibroin hydrogels with extracellular matrix-mimicking cues of mechanical properties and RGD (Arg-Gly-Asp) signals are gelled in situ to fill the lesion site to modulate injury-induced neuroinflammation and promote neurite regrowth after SCI. The bionic hydrogel system provides biomimetic mechanical cues to promote neuronal differentiation of neural stem/progenitor cells (NPCs) and neurite growth by activating YAP nuclear expression. Importantly, favored by the strong capacity of silk fibroin hydrogels on macrophage/microglia recruitment, NPCs encapsulated hydrogel (NPCs@SFRGD0.1) effectively promotes recruited macrophages/microglia to M2 polarization in the lesion site by releasing S100A4 and thereby remodels the inflammatory microenvironment after SCI. Moreover, NPCs@SFRGD0.1 successfully reduces glial scar formation and accelerates corticospinal tract axon regrowth to improve locomotor recovery. Overall, this work contributes to illustrating the therapeutic mechanism of NPCs development based biomaterial therapies on modulating inflammatory microenvironment and this NPCs enhanced silk fibroin hydrogel provides a promising therapeutic strategy for SCI.     

A Stable Polymer-based Solid-State Lithium Metal Battery and its Interfacial Characteristics Revealed by Cryogenic Transmission Electron Microscopy

Solid-state lithium metal batteries (SSLMBs) are a promising candidate for next-generation energy storage systems due to their intrinsic safety and high energy density. However, they still suffer from poor interfacial stability, which can incur high interfacial resistance and insufficient cycle lifespan. Herein, a novel poly(vinylidene fluoride‑hexafuoropropylene)-based polymer electrolyte (PPE) with LiBF₄ and propylene carbonate plasticizer is developed, which has a high room-temperature ionic conductivity up to 1.15 × 10⁻³ S cm⁻¹ and excellent interfacial stability. Benefitting from the stable interphase, the PPE-based symmetric cell can operate for over 1000 h. By virtue of cryogenic transmission electron microscopy (Cryo-TEM) characterization, the high interfacial compatibility between Li metal anode and PPE is revealed. The solid electrolyte interphase is made up of an amorphous outer layer that can keep intimate contact with PPE and an inner Li₂O-dominated layer that can protect Li from continuous side reactions during battery cycling. A LiF-rich transition layer is also discovered in the region of PPE close to Li metal anode. The feasibility of investigating interphases in polymer-based solid-state batteries via Cryo-TEM techniques is demonstrated, which can be widely employed in future to rationalize the correlation between solid-state electrolytes and battery performance from ultrafine interfacial structures.     

An Intrinsically Nonflammable Electrolyte for Prominent-Safety Lithium Metal Batteries with High Energy Density and Cycling Stability

Nex-generation high-energy-density storage battery, assembled with lithium (Li)-metal anode and nickel-rich cathode, puts forward urgent demand for advanced electrolytes that simultaneously possess high security, wide electrochemical window, and good compatibility with electrode materials. Herein an intrinsically nonflammable electrolyte is designed by using 1 M lithium difluoro(oxalato)borate (LiDFOB) in triethyl phosphate (TEP) and N-methyl-N-propyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide [Pyr₁₃][TFSI] ionic liquid (IL) solvents. The introduction of IL can bring plentiful organic cations and anions, which provides a cation shielding effect and regulates the Li⁺ solvation structure with plentiful Li⁺-DFOB⁻ and Li⁺-TFSI⁻ complexes. The unique Li⁺ solvation structure can induce stable anion-derived electrolyte/electrode interphases, which effectively inhibit Li dendrite growth and suppress side reactions between TEP and electrodes. Therefore, the LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90)/Li coin cell with this electrolyte can deliver stable cycling even under 4.5 V and 60 °C. Moreover, a Li-metal battery with thick NCM90 cathode (≈ 15 mg cm⁻²) and thin Li-metal anode (≈ 50 µm) (N/P ≈ 3), also reveals stable cycling performance under 4.4 V. And a 2.2 Ah NCM90/Li pouch cell can simultaneously possess prominent safety with stably passing the nail penetration test, and high gravimetric energy density of 470 Wh kg⁻¹ at 4.4 V.     

Antioxidant High-Conductivity Copper Pastes Based on Core–Shell Copper Nanoparticles for Flexible Printed Electronics

As a nontoxic and cost-effective material, copper pastes have attracted great attention in both academia and industry. However, achieving the long-term stability of copper pastes remains challenging due to their susceptibility to oxidation. Therefore, stable copper nanoparticles with a Cu(0)–Cu(I) core–shell structure containing a surface passivation layer of formate ions-involved Cu(I) coordination polymers are developed. Based on the self-reducing nature of the passivation layer, the nanoparticle-based copper pastes can be sintered in <1 min, showing high electrical conductivity (220 000 S cm⁻¹), mechanical flexibility, and long-term stability after sintering. The excellent properties of the developed copper pastes are even comparable with the ones of silver pastes. These stable copper pastes have broad applications in printed electronics (e.g., glucose sensors, RFID tags, and electromagnetic shielding films), showing great potential in the fabrication of flexible printed electronics.     

Spidermen Strategy for Stable 24% Efficiency Perovskite Solar Cells

The interface energetics-modification plays an important role in improving the power conversion efficiency (PCE) among the perovskite solar cells (PSCs). Considering the low carrier mobility caused by defects in PSCs, a double-layer modification engineering strategy is adopted to introduce the “spiderman” NOBF₄ (nitrosonium tetrafluoroborate) between tin dioxide (SnO₂ and perovskite layers. NO⁺, as the interfacial bonding layer, can passivate the oxygen vacancy in SnO₂, while BF₄⁻ can optimize the defects in the bulk of perovskite. This conclusion is confirmed by theoretical calculation and transmission electron microscopy (TEM). The synergistic effect of NO⁺ and BF₄⁻ distinctly heightens the carrier extraction efficiency, and the PCE of PSCs is 24.04% with a fill factor (FF) of 82.98% and long-term stability. This study underlines the effectiveness of multifunctional additives in improving interface contact and enhancing PCE of PSCs.     

Vapor Phase Dealloying Derived Nanoporous Co@CoO/RuO2 Composites for Efficient and Durable Oxygen Evolution Reaction (Adv. Funct. Mater. 17/2023)

The development of low-cost and effective oxygen evolution reaction (OER) electrocatalysts to expedite the slow kinetics of water splitting is crucial for increasing the efficiency of energy conversion from electricity to hydrogen fuel. Herein, 3D bicontinuous nanoporous Co@CoO/RuO₂ composites with tunable sizes and chemical compositions are fabricated by introducing vapor phase dealloying of cobalt-based alloys. The influence of physical parameters on the formation of nanoporous Co substrates with various feature ligament sizes is systematically investigated. The CoO/RuO₂ shell is constructed by integrating a thin layer of RuO₂ on the inner surface of nanoporous Co, where the CoO interlayer is formed by annealing oxidization. The composite catalyst delivers an ultralow overpotential of 198 mV at 10 mA cm⁻², Tafel slope of 57.1 mV dec⁻¹, and long-term stability of 50 h. The superior OER activity and fast reaction kinetics are attributed to charge transfer through the coupling of Co O Ru bonds at the interface and the excellent nanopore connectivity, while the durability originates from the highly stable CoO/RuO₂ interface.     

Leveraging Bioinspired Structural Constraints for Tunable and Programmable Snapping Dynamics in High-Speed Soft Actuators

Creating high-speed soft actuators will have broad engineering and technological applications. Snapping provides a power-amplified mechanism to achieve rapid movements in soft actuators that typically show slow movements. However, precise control of snapping dynamics (e.g., speed and direction of launching or jumping) remains a daunting challenge. Here, a bioinspired design principle is presented that harnesses a reconfigurable constraint structure integrated into a photoactive liquid crystal elastomer actuator to enable tunable and programmable control over its snapping dynamics. By reconfiguring constrained fin-array-shaped structure, the snapping dynamics of the structured actuator, such as launching or jumping angle and height, motion speed, and release force can be on-demand tuned, thus enabling controllable catapult motion and programmable jumping. Moreover, the structured actuators exhibit a unique combination of ultrafast moving speed (up to 2.5 m s⁻¹ in launching and 0.22 m s⁻¹ in jumping), powerful ejection (long ejection distance of ≈20 cm, 35 mg ball), and high jumping height (≈8 cm, 40 times body lengths), which few other soft actuators can achieve. This study provides a new universal design paradigm for realizing controllable rapid movements and high-power motions in soft matter, which are useful for building high-performance soft robotics and actuation devices.