All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional l...All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional liquid-state LIBs. However, the practical success of ASLS-LIBs is bottlenecked by the lack of advanced separator technology that can simultaneously realize high performances in puncturing-tolerability,fire-resistance, and importantly, wetting-capability with non-flammable liquid-electrolytes. Here, we propose a concept of inorganic in-situ separator(IISS) by hybrid-sol physical crosslinking directly onto the electrode surface to address the above challenges. Particularly, the hybrid-sol is designed with silica nanoparticles as the building block and poly(vinylidene difluoride) nanoparticles as the crosslinking agent. The critical factors for controlling the IISS microstructures and properties have been systematically investigated. The advantages of the IISS have been confirmed by its fast wetting with various fireresistant liquid-electrolytes, customizable thickness and porous structures, robust interface with planar or three-dimensional(3D)-structured electrodes, and importantly, unexpected self-adaptability against puncturing. Enabled by the above merits, a fire-resistant ASLS-LIB is successfully assembled and demonstrated with stable electrochemical performance. This sol-crosslinked IISS may open an avenue for the studies on the next-generation separator technology, cell assembling, solid electrolyte processing as well as non-flammable secondary batteries.展开更多
The synthesis of a new azobenzene(azo)-containing main-chain crystalline polymer with reactive secondary amino groups in its backbone and photodeformation behaviors of its supramolecular hydrogen-bonded fibers are des...The synthesis of a new azobenzene(azo)-containing main-chain crystalline polymer with reactive secondary amino groups in its backbone and photodeformation behaviors of its supramolecular hydrogen-bonded fibers are described. This main-chain azo polymer(namely Azo-MP6) was prepared via first the synthesis of a diacrylate-type azo monomer and its subsequent Michael addition copolymerization with trans-1,4-cyclohexanediamine under a mild reaction condition. Azo-MP6 was found to have a linear main-chain chemical structure instead of a branched one, as verified by comparing its ~1H-NMR spectrum with that of the azo polymer prepared via the polymer analogous reaction of AzoMP6 with acetic anhydride. The thermal stability, phase transition behavior, and photoresponsivity of Azo-MP6 were characterized with TGA,DSC, POM, XRD, and UV-Vis spectroscopy. The experimental results revealed that it had good thermal stability, low glass transition temperature,broad crystalline phase temperature range, and highly reversible photoresponsivity. Physically crosslinked supramolecular hydrogen-bonded fibers with good mechanical properties and a high alignment order of azo mesogens were readily fabricated from Azo-MP6 by using the simple melt spinning method, and they could show "reversible" photoinduced bending under the same UV light irradiation and good anti-fatigue properties.展开更多
Recently,a number of studies reported that casein was composed of various multifunctional bioactive peptides such as casein phosphopeptide andβ-casochemotide-1 that bind calcium ions and induce macrophage chemotaxis,...Recently,a number of studies reported that casein was composed of various multifunctional bioactive peptides such as casein phosphopeptide andβ-casochemotide-1 that bind calcium ions and induce macrophage chemotaxis,which is crucial for bone homeostasis and bone fracture repair by cytokines secreted in the process.We hypothesized that the effects of the multifunctional biopeptides in casein would contribute to improving bone regeneration.Thus,we designed a tissue engineering platform that consisted of casein and polyvinyl alcohol,which was a physical-crosslinked scaffold(milk-derived protein;MDP),via simple freeze-thaw cycles and performed surface modification using 3,4-dihydroxy-L-phenylalanine(DOPA),a mussel adhesive protein,for immobilizing adhesive proteins and cytokines for recruiting cells in vivo(MDP-DOPA).Both the MDP and MDP-DOPA groups proved indirectly contribution of macrophages migration as RAW 264.7 cells were highly migrated toward materials by contained bioactive peptides.We implanted MDP and MDP-DOPA in a mouse calvarial defect orthotopic model and evaluated whether MDP-DOPA showed much faster mineral deposition and higher bone density than that of the no-treatment and MDP groups.The MDP-DOPA group showed the accumulation of host M2 macrophages and mesenchymal stem cells(MSCs)around the scaffold,whereas MDP presented mostly M1 macrophages in the early stage.展开更多
基金National Natural Science Foundation of China (52203123)Sichuan Science and Technology Program (2023NSFSC0991)+2 种基金State Key Laboratory of Polymer Materials Engineering (sklpme-2023-1-05 and sklpme-2024-2-04)Fundamental Research Funds for the Central UniversitiesThis research was also partially sponsored by the Double First-Class Construction Funds of Sichuan University。
文摘All-safe liquid-state lithium-ion batteries(ASLS-LIBs) is of great interest as they can potentially combine the safety of all-solid-state batteries with the high performance and low manufacturing cost of traditional liquid-state LIBs. However, the practical success of ASLS-LIBs is bottlenecked by the lack of advanced separator technology that can simultaneously realize high performances in puncturing-tolerability,fire-resistance, and importantly, wetting-capability with non-flammable liquid-electrolytes. Here, we propose a concept of inorganic in-situ separator(IISS) by hybrid-sol physical crosslinking directly onto the electrode surface to address the above challenges. Particularly, the hybrid-sol is designed with silica nanoparticles as the building block and poly(vinylidene difluoride) nanoparticles as the crosslinking agent. The critical factors for controlling the IISS microstructures and properties have been systematically investigated. The advantages of the IISS have been confirmed by its fast wetting with various fireresistant liquid-electrolytes, customizable thickness and porous structures, robust interface with planar or three-dimensional(3D)-structured electrodes, and importantly, unexpected self-adaptability against puncturing. Enabled by the above merits, a fire-resistant ASLS-LIB is successfully assembled and demonstrated with stable electrochemical performance. This sol-crosslinked IISS may open an avenue for the studies on the next-generation separator technology, cell assembling, solid electrolyte processing as well as non-flammable secondary batteries.
基金financially supported by the National Natural Science Foundation of China (Nos. 21574070 and 21774063)Natural Science Foundation of Tianjin (No. 16JCZDJC36800)
文摘The synthesis of a new azobenzene(azo)-containing main-chain crystalline polymer with reactive secondary amino groups in its backbone and photodeformation behaviors of its supramolecular hydrogen-bonded fibers are described. This main-chain azo polymer(namely Azo-MP6) was prepared via first the synthesis of a diacrylate-type azo monomer and its subsequent Michael addition copolymerization with trans-1,4-cyclohexanediamine under a mild reaction condition. Azo-MP6 was found to have a linear main-chain chemical structure instead of a branched one, as verified by comparing its ~1H-NMR spectrum with that of the azo polymer prepared via the polymer analogous reaction of AzoMP6 with acetic anhydride. The thermal stability, phase transition behavior, and photoresponsivity of Azo-MP6 were characterized with TGA,DSC, POM, XRD, and UV-Vis spectroscopy. The experimental results revealed that it had good thermal stability, low glass transition temperature,broad crystalline phase temperature range, and highly reversible photoresponsivity. Physically crosslinked supramolecular hydrogen-bonded fibers with good mechanical properties and a high alignment order of azo mesogens were readily fabricated from Azo-MP6 by using the simple melt spinning method, and they could show "reversible" photoinduced bending under the same UV light irradiation and good anti-fatigue properties.
基金supported by the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(2020R1A6A3A01098495,2020R1A6A1A03043283)by the Bio&Medical Technology Development Program of the National Research Foundation(NRF)funded by the Korean government(MSIT)(2018M3A9E2023259)supported by Basic Science Research Capacity Enhancement Project through Korea Basic Science Institute(National research Facilities and Equipment Center)grant funded by the Ministry of Education(2019R1A6C1010033).
文摘Recently,a number of studies reported that casein was composed of various multifunctional bioactive peptides such as casein phosphopeptide andβ-casochemotide-1 that bind calcium ions and induce macrophage chemotaxis,which is crucial for bone homeostasis and bone fracture repair by cytokines secreted in the process.We hypothesized that the effects of the multifunctional biopeptides in casein would contribute to improving bone regeneration.Thus,we designed a tissue engineering platform that consisted of casein and polyvinyl alcohol,which was a physical-crosslinked scaffold(milk-derived protein;MDP),via simple freeze-thaw cycles and performed surface modification using 3,4-dihydroxy-L-phenylalanine(DOPA),a mussel adhesive protein,for immobilizing adhesive proteins and cytokines for recruiting cells in vivo(MDP-DOPA).Both the MDP and MDP-DOPA groups proved indirectly contribution of macrophages migration as RAW 264.7 cells were highly migrated toward materials by contained bioactive peptides.We implanted MDP and MDP-DOPA in a mouse calvarial defect orthotopic model and evaluated whether MDP-DOPA showed much faster mineral deposition and higher bone density than that of the no-treatment and MDP groups.The MDP-DOPA group showed the accumulation of host M2 macrophages and mesenchymal stem cells(MSCs)around the scaffold,whereas MDP presented mostly M1 macrophages in the early stage.
