Strategically constructed AlGaN doping barriers for efficient deep ultraviolet light-emitting diodes: erratum.

We present an erratum to our Letter [Opt. Lett.49, 2049 (2024)10.1364/OL.522212]. There is a careless omission of some references because our Letter is longer than the maximum allowed four pages. The missing references and their specific quote location are listed in the following. These corrections do not affect the data plotted in figures, discussion, or conclusion of the original Letter.

Dual-functional Separators Regulating Ion Transport Enabled by 3D-Reinforced Polyimide Microspheres Protective Layer for Dendrite-Free and High-Temperature Lithium Metal Batteries.

High-energy-density lithium metal batteries (LMBs) are confronted with crucial concerns of security and a short cycle lifespan caused by the uncontrollable formation of lithium (Li) dendrites. The poor thermal stability and heterogeneous Li deposition of conventional polyolefin separators often cause battery short circuiting and thermal runaway in LMBs. Herein, a novel dual-functional PE composite separator (PI-COOH/PE) coated by carboxyl polyimide (PI) microspheres is fabricated by an etching-acidification method. The three-dimensional (3D) high-temp PI microsphere with rich carboxyl groups on the surface improve the security of LMBs at extremely high temperatures and facilitate the formation of a stable and uniform SEI layer, which contributes to accelerating the Li+ transport and stabilizing the formation of the SEI layer. Consequently, the Li symmetric cell assembled with the (PI-COOH)/PE separator exhibits stable overpotential over 3000 h, and the corresponding Li//NCM811 full cells also show a high-level discharge capacity of 146.6 mAh g-1 at 5 C. Meanwhile, it also demonstrates outstanding cycling stability and thermal safety, which can survive continuously over 160 min at 140 °C (vs 21 min for PE). The above results indicate the (PI-COOH)/PE separator constructed by a low-cost and industrial-friendly strategy simultaneously addresses high-temperature stability and dendrite resistance.

Improving Interfacial and Compressive Properties of Polyimide Fiber by Constructing Inorganic Layers on Fiber Surface.

The compressive performance of organic fiber has always been a key problem, limiting its development. In this paper, silicon oxide, alumina, and titanium oxide particles were separately deposited on the surface of high-strength and high-modulus polyimide (PI) fibers to form a structural supporting shell by using a magnetron sputtering method. The theoretical thickness was calculated by thermogravimetric analysis in good agreement with the actual thickness determined from scanning electron microscopy. The mechanics, surface, and interface properties of the measured fibers were analyzed mainly from the aspects of surface energy, interfacial shear strength (IFSS), and compression strength. The results showed that after magnetron sputtering, the inorganic shells were uniformly deposited on the surface of PI fiber, resulting in an increase in the content of inorganic elements as well as the roughness. As a result, the surface energy and IFSS of silica-coated fiber was increased by 174 and 85.6%, respectively, and compression strength was increased by 45.7%. This study provides a new approach for improving the interface property and compression strength of high-strength and high-modulus PI-fiber-reinforced composites.

Strategically constructed AlGaN doping barriers for efficient deep ultraviolet light-emitting diodes.

Here, we propose a sandwich-like Si-doping scheme (undoped/Si-doped/undoped) in Al0.6Ga0.4N quantum barriers (QBs) to simultaneously promote the optoelectronic performances and reliability of deep ultraviolet light-emitting diodes (DUV-LEDs). Through experimental and numerical analyses, in the case of DUV-LEDs with conventional uniform Si-doping QB structure, severe operation-induced reliability degradation, including the increase of reverse leakage current (IR) and reduction of light output power (LOP), will offset the enhancement of optoelectronic performances as the Si-doping levels increase to an extent, which hinders further development of DUV-LEDs. According to a transmission electron microscope characterization and a numerical simulation, an improved interfacial quality in multiple quantum wells (MQWs) and more uniform carrier distribution within MQWs are demonstrated for our proposed Si-doping structure in comparison to the uniform Si-doping structure. Consequently, the proposed DUV-LED shows superior wall-plug efficiency (4%), IR at -6 V reduced by almost one order of magnitude, and slower LOP degradation after 168-h 100 mA-current-stress operation. This feasible doping scheme provides a promising strategy for the high-efficiency and cost-competitive DUV-LEDs.

Enhanced performance of 275-nm AlGaN-based deep-ultraviolet LEDs via internal-roughed sapphire and SiO2-antireflection film.

The internal-roughed sapphire in a 275-nm AlGaN-based deep-ultraviolet (DUV) LED is fabricated using a laser stealth dicing technique to improve the high-angle extraction. Furthermore, the low-angle extraction is enhanced by depositing a SiO2-antireflection film on the internal-roughed sapphire surface. Compared with conventional DUV LEDs with a light output power (LOP) of 33.05 mW at 350 mA, the LOP of DUV LEDs with internal-roughed sapphire and SiO2-antireflection film increases by 20.85% to 39.94 mW. In addition, combined with finite-difference time-domain simulations, the effect of internal-roughed sapphire on the transmission and light extraction efficiency (LEE) of the DUV LEDs is revealed. The combination of the internal-roughed sapphire substrate and SiO2-antireflection film improves the LEEs of transverse electric (TE) and transverse magnetic (TM) polarized light by 1.6% and 108%, respectively. These results offer the potential for large-scale, low-cost industrial production of high-efficiency DUV LEDs.

Dietary alfalfa powder supplementation improves growth and development, body health, and meat quality of Tibetan sheep.

The application of alfalfa powder (AP) in Tibetan sheep to explore its healthy effects and meat quality improvement potential has not been reported. Our study found that AP improved the growth performance, serum metabolism, and antioxidation of Tibetan sheep. The edible quality, sensory quality, and nutritional quality of longissimus dorsi (LD) were analyzed. We observed lower drip loss and hue angle of meat after AP supplementation. AP also increased the cooked meat percentage, pH24h, a*24h, chroma24h, and the contents of protein and fat. The targeted metabolomics profiling revealed that the contents of essential amino acids and flavor amino acids in mutton increased by AP treatments. AP also promoted the deposition of MUFA and PUFA. Therefore, as a promising botanical supplement, AP has a positive effect on the growth, development, and body health of Tibetan sheep, and is also conductive to providing healthy and nutritious high-quality livestock products.

Thermostable and nonflammable polyimide/zirconia compound separator for lithium-ion batteries with superior electrochemical and safe properties.

Separators are applied to segregate cathode and anode, and provide ion transport channels in lithium-ion batteries (LIBs). Nevertheless, present commercial polyolefin separators represent high thermal shrinkage and inferior electrolyte wettability, seriously limiting wider development of LIBs. In this work, we prepared zirconia (ZrO2) nanolayer encapsulated polyimide (PI) nanofiber compound separator through in-situ polar adsorption and hydrolysis strategy. The obtained PI/ZrO2 compound separator has superior thermal stability, electrolyte wettability and flame retardance in comparison with polypropylene (PP) separator. The shrinkage ratio of prepared PI/ZrO2 compound separator is 0 even at 300 °C, while the PP separator significantly shrank at 160 °C. Furthermore, the ionic conductivity of PI/ZrO2 separator reaches up to 1.32 mS cm-1, far higher than 0.34 mS cm-1 of PP separator. Besides, the coin batteries of LiNi0.8Co0.1Mn0.1O2 (NCM811)/electrolyte-separator/lithium (Li) assembled with PI/ZrO2 compound separator exhibit enhanced rate performance, high discharge capacity retention rate of 88.3% after 100 cycles at 1C and excellent battery safety performance even at 140 °C. Thus, combined with its advantages, such as preparation, thermostability, electrolyte wettability, electrochemical property and safety, the PI/ZrO2 compound separator exhibits promising prospect in the application of commercial LIBs.

High-Temperature-Induced Shape Memory Copolyimide.

A series of polyimide (PI) films with a high-temperature-induced shape memory effect and tunable properties were prepared via the facile random copolymerization of 4,4'-oxydianiline (ODA) with 4,4'-(hexafluoroisopropyl)diphthalic anhydride (6FDA) and 4,4'-oxydiphthalic anhydride (ODPA). The trigger temperature can be controlled from 294 to 326 °C by adjusting the ratio of monomers. The effects of monomer rigidity on the chain mobility, physical properties, and shape memory performance of as-prepared copolyimide were systematically investigated. The introduction of ODPA could enhance the mobility of PI macromolecular chains, which made chain entanglement more likely to occur and increased the physical crosslinking density, thereby improving the PI's shape recovery up to 97%. Meanwhile, the existence of 6FDA enabled PI films to set quickly at low temperatures with a shape fixation of 98%. The shape memory cycling characteristics of the polyimide films are also studied, and the relationship between the PI chemical structure and the film properties are further discussed.

Revealing the High-Modulus Mechanism of Polyimide Films Prepared with 3,4'-ODA.

To prepare PIs (polyimides) with desirable thermal and mechanical properties is highly demanded due to their widespread applications in flexible optoelectronic devices and printed circuit boards. Here, the PI films of BPDA/4,4'-ODA, BPDA/3,4'-ODA, PMDA/4,4'-ODA, PMDA/3,4'-ODA systems were prepared, and it was found that the PIs with 3,4'-ODA always exhibit a high modulus compared with the PIs with 4,4'-ODA. To disclose the mechanism of high-modulus PI films with 3,4'-ODA, amorphous PI models and uniaxial drawing PI models were established and calculated based on MD simulation. The PI structural deformations at different length scales, i.e., molecular chain cluster scale and repeat unit scale, under the same stress were detailed and analyzed, including the variation of chain conformation, bond length, bond angle, internal rotation energy, and torsion angle. The results indicate that PIs with 3,4-ODA have higher internal rotation energy and smaller deformation with the same stress, consistent with the high modulus.

Enhanced Impact Properties of Hybrid Composites Reinforced by Carbon Fiber and Polyimide Fiber.

A series of hybrid fiber-reinforced composites were prepared with polyimide fiber and carbon fiber as the reinforcement and epoxy resin as the matrix. The influence of stacking sequence on the Charpy impact and flexural properties of the composites as well as the failure modes were studied. The results showed that hybrid fiber-reinforced composites yielded nearly 50% increment in Charpy impact strength compared with the ones reinforced by carbon fiber. The flexural performance was significantly improved compared with those reinforced solely by polyimide fibers and was greatly affected by the stacking sequence. The specimens with compressive sides distributed with carbon fiber possessed higher flexural strength, while those holding a sandwich-like structure with carbon fiber filling between the outer layers displayed a higher flexural modulus.

Effect of a "Zn Bridge" on the Consecutively Tunable Retention Characteristics of Volatile Random Access Memory Materials.

Polyimide memory materials with a donor-acceptor structure based on a charge-transfer mechanism exhibit great potential for next-generation information storage technology due to their outstanding high-temperature resistance and good dimensional and chemical stability. Precisely controlling memory performance by limited chemical decoration is one of core challenges in this field. Most reported work mainly focuses on designing novel and elaborate electron donors or acceptors for the expected memory behavior of polyimides; this takes a lot of time and is not always efficacious. Herein, we report a series of porphyrinated copolyimides coPI-Znx (x=5, 10, 20, 50, 80), where x represents the mole percentage of Zn ion in the central core of the porphyrin. Experimental and theoretical analysis indicate that the Zn ion could play a vital bridge role in promoting the formation and stabilization of a charge-transfer complex by enhancing the hybridization of local and charge transfer (HLCT) excitations of porphyrinated polyimides, endowing coPI-Znx with volatile random access memory performance and continuously tunable retention time. This work could provide one simple strategy to precisely regulate memory performance merely by altering the metal content in porphyrinated polyimides.

In-Situ Synthesis of N, O, P-Doped Hierarchical Porous Carbon from Poly-bis(phenoxy)phosphazene for Polysulfide-Trapping Interlayer in Lithium-Sulfur Batteries.

The shuttling of polysulfides is the most detrimental contribution to degrading the capacity and cycle stability of lithium-sulfur (Li-S) batteries. Adding a carbon interlayer to prevent the polysulfides from migrating is feasible, and a rational design of the structures and surface properties of the carbon layer is essential to increasing its effectiveness. Herein, we report a hierarchical porous carbon (HPC) created by carbonization of bis(phenoxy)phosphazene and in-situ doping of triple heteroatoms into the carbon lattice to fabricate an effective polysulfide-trapping interlayer. The generated carbon integrates the advantages of a hierarchical porous structure, a high specific area and rich dopants (N, O and P), to yield chemisorption and physical confinement for polysulfides and fast ion-transport synergistically. The HPC interlayer significantly improves the electrochemical performance of Li-S batteries, including an exceptional discharge capacity of 1509 mA h/g at 0.06 C and a high capacity retention of 83.7 % after 250 cycles at 0.3 C. This work thus proposes a facile in-situ synthesis of heteroatom-doped carbon with rational porous structures for suppressing the shuttle effect.

Zinc Ion Triggered Controllable Binary/Ternary Memory Conversion Behaviors in Polyimides Containing Pendant Porphyrin Group.

Compared with typical binary polymeric memory materials, functional polymers with ternary memory performance possess significant potential to achieve ultra-high-density data storage. The reported ternary memory polymers are normally driven by dual-mechanism. However, the involved thermodynamically unstable mechanisms (field-induced conformation change or conductive filament formation/fracture) may result in the poor reliability of memory devices under high-temperature working atmosphere. Another strategy to realize ternary memory is introducing charge trapping/de-trapping mechanism by attaching charge trap atom/group at electron donor, which is proved not always effective. Moreover, the synergistic two mechanisms may have difficulty for clarifying the relationship between memory performance and chemical structures, which is the core issue of polymer memory materials. Besides, some multi-level memory materials need the cooperative participation of artificially setting compliance current, which is the extension of typical binary memory and may cause a more complicated technique and logic circuit. Herein, based on charge-transfer mechanism, a concise and effective strategy to realize ternary memory application is proposed. By inserting a Zn ion, the charge-transfer process occurring in electron donors can lead to the novel electrical tri-stability memory behaviors. This work can provide a novel idea for achieving reliable and intrinsic ternary high-density data storage applications.

Structural Evolution of Macromolecular Chain During Pre-imidization Process and Its Effects on Polyimide Film Properties.

Pre-imidization has been found to have a determining role on the final properties of polyimide (PI) films. In this work, a series of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)/2,2'-bis(trifluoromethyl)benzidine (TFMB) PI models with specified pre-imidization degree (pre-ID) were constructed and analyzed on the basis of molecular dynamic (MD) simulation to reveal the real-time evolution of structure and properties that occurred during the pre-imidization process. The MD results indicated that the Tg of the models increased obviously with increasing pre-ID, which corresponded to the increase of rigid PI chain segments that restricted the mobility of molecular chains. In addition, the increase of fractional free volume and mean square end-to-end distance indicated looser chain packing and more extended chain conformation during the pre-imidization process. As a further verification, a series of corresponding PI films were experimentally prepared via a controlled partially pre-imidization process. Mechanical properties of the prepared PI films were tested to be significantly enhanced, and the coefficient of thermal expansion decreased from 61.5 to 47.6 ppm/°C with pre-ID increasing from 0% to 100%, which could be attributed to the orderly molecular chain arrangement formed during the chemical pre-imidization process, as disclosed by MD simulation. This work paves the way for the observation of the real-time structure and property evolutions of PI materials, especially during the pre-imidization process.

A Janus nanofiber-based separator for trapping polysulfides and facilitating ion-transport in lithium-sulfur batteries.

Endowing separators with the polysulfide-blocking function is urgently needed for high-performance lithium-sulfur (Li-S) batteries. Thus far, most of the reported research has focused on modifying conventional polyolefin separators but with poor thermal stability and low ionic conductivity. To address these issues, herein we report a Janus separator based on a thermally stable polymeric nanofabric designed with abilities to trap polysulfides and facilitate the transport of Li+ simultaneously. This Janus separator possesses a configuration of a carbon nanofiber (CNF) layer toward the sulfur cathode and the polyimide (PI) nanofabric toward the Li metal anode. It is demonstrated that the conductive CNF layer can effectively anchor and convert the polysulfides; meanwhile, the excellent wettability with liquid electrolytes and the highly porous structure of the PI nanofiber layer significantly promote the Li+-transport. In addition, the Janus separator presents notable advantages in thermal dimensional stability benefiting from the PI nanofabric. As a result, the Li-S battery armed with the Janus separator shows a high initial capacity (1393 mA h g-1 at 0.1 A g-1), stable cycling performance (822 mA h g-1 at 1 A g-1) and high coulombic efficiency of 99.6%.

The design of a multifunctional separator regulating the lithium ion flux for advanced lithium-ion batteries.

Herein, we design a controllable approach for preparing multifunctional polybenzimidazole porous membranes with superior fire-resistance, excellent thermo-stability, and high wettability. Specifically, the recyclable imidazole is firstly utilized as the eco-friendly template for micropores formation, which is an interesting finding and has tremendous potential for low-cost industrial production. The unique backbone structure of the as-prepared polybenzimidazole porous membrane endows the separator with superb thermal dimensional stability at 300 °C. Most significantly, the inherent flame retardancy of polybenzimidazole can ensure the high security of lithium-ion batteries, and the existence of polar groups of imidazole can regulate the Li+ flux and improve the ionic conductivity of lithium ions. Notably, the cell with a polybenzimidazole porous membrane presents higher capability (131.7 mA h g-1) than that of a commercial Celgard membrane (95.4 mA h g-1) at higher charge-discharge density (5C), and it can work normally at 120 °C. The fascinating comprehensive properties of the polybenzimidazole porous membrane with excellent thermal-stability, satisfying wettability, superb flame retardancy and good electrochemical performance indicate its promising application for high-safety and high-performance lithium-ion batteries.

In Situ Armoring: A Robust, High-Wettability, and Fire-Resistant Hybrid Separator for Advanced and Safe Batteries.

Development of nonflammable separators with excellent properties is in urgent need by next-generation advanced and safe energy storage devices. However, it has been extremely challenging to simultaneously achieve fire resistance, high mechanical strength, good thermomechanical stability, and low ion-transport resistance for polymeric separators. Herein, to address all these needs, we report an in situ formed silica@silica-imbedded polyimide (in situ SiO2@(PI/SiO2)) nanofabric as a new high-performance inorganic-organic hybrid separator. Different from conventional ceramics-modified separators, this in situ SiO2@(PI/SiO2) hybrid separator is realized for the first time via an inverse in situ hydrolysis process. Benefiting from the in situ formed silica nanoshell, the in situ SiO2@(PI/SiO2) hybrid separator shows the highest tensile strength of 42 MPa among all reported nanofiber-based separators, excellent wettability to the electrolyte, good thermomechanical stability at 300 °C, and fire resistance. The LiFePO4 half-cell assembled with this hybrid separator showed a high capacity of 139 mAh·g-1@5C, which is much higher than that of the battery with the pristine PI separator (126.2 mAh·g-1@5C) and Celgard-2400 separator (95.1 mAh·g-1@5C). More importantly, the battery showed excellent cycling stability with no capacity decay over 100 cycles at the high temperature of 120 °C. This study provides a novel method for the fabrication of high-performance and nonflammable polymeric-inorganic hybrid battery separators.

Robust polyimide nanofibrous membrane with porous-layer-coated morphology by in situ self-bonding and micro-crosslinking for lithium-ion battery separator.

Herein, we demonstrate a strategy to improve the tensile strength, thermal safety issues, and electrochemical performance of an as-synthesized polyimide separator. By spraying the solution of a specific chemical constituent on both sides of a poly(amic acid) non-woven membrane followed by thermal treatment, a novel polyimide nanofibrous membrane with porous-layer-coated morphology was successfully fabricated by in situ self-bonding and micro-crosslinking technique. The self-bonding and micro-crosslinking techniques improve the tensile strength of the nanofiber membranes from 5 MPa to 28 MPa by forming a crosslinked network structure, thereby reducing the risk of nanofiber disassembly during long-term operation. The rigid structure and aromatic groups in the polyimide chain enable the separator to have outstanding thermal dimensional stability at temperatures as high as 300 °C and thermal stability (5% weight loss at about 528 °C). Additionally, the unique flame retarding capability of polyimide ensures high security of the battery as well. Notably, the lithium-ion battery using porous-layer-coated polyimide separator exhibits a much higher capability (129.9 mA h g-1, 5C) than that using a Celgard-2400 separator (95.2 mA h g-1, 5C) and could work steadily at 120 °C, thus implying promising application in next generation high-safety and high-performance lithium-ion batteries.

Preparation of Palladium/Silver-Coated Polyimide Nanotubes: Flexible, Electrically Conductive Fibers.

A simple and practical method for coating palladium/silver nanoparticles on polyimide (PI) nanotubes is developed. The key steps involved in the process are silver ion exchange/reduction and displacement reactions between silver and palladium ions. With the addition of silver, the conductivity of the PI nanotubes is greatly enhanced. Further, the polyimide nanotubes with a dense, homogeneous coating of palladium nanoparticles remain flexible after heat treatment and show the possibility for use as highly efficient catalysts. The approach developed here is applicable for coating various noble metals on a wide range of polymer matrices, and can be used for obtaining polyimide nanotubes with metal loaded on both the inner and outer surface.

Shackling Effect Induced Property Differences in Metallo-Supramolecular Polymers.

We demonstrate here the synthesis of a novel class of metallo-supramolecular polymers with shackled structure, via the coordination of cyclic di(bis-terpyridine-triphenyl ether ester) ligands with ruthenium(II) ions. The constraint from the ring topology via the shackling of ligands provides novel properties to these metallo-supramolecular polymers, including the formation of dendritic crystals, red-shift of absorption bands in the UV-vis spectra from interchain charge-transfer transitions, and a typical flash-type memory behavior.