Chitosan is a product of the deacetylation of chitin, which is widely found in nature. Chitosan is insoluble in water and most organic solvents, which seriously limits both its application scope and applicable fields. However, chitosan contains active functional groups that are liable to chemical reactions; thus, chitosan derivatives can be obtained through the chemical modification of chitosan. The modification of chitosan has been an important aspect of chitosan research, showing a better solubility, pH-sensitive targeting, an increased number of delivery systems, etc. This review summarizes the modification of chitosan by acylation, carboxylation, alkylation, and quaternization in order to improve the water solubility, pH sensitivity, and the targeting of chitosan derivatives. The applications of chitosan derivatives in the antibacterial, sustained slowly release, targeting, and delivery system fields are also described. Chitosan derivatives will have a large impact and show potential in biomedicine for the development of drugs in future.
Composite electrolytes are widely studied for their potential in realizing improved ionic conductivity and electrochemical stability. Understanding the complex mechanisms of ion transport within composites is critical for effectively designing high-performance solid electrolytes. This study examines the compositional dependence of the three determining factors for ionic conductivity, including ion mobility, ion transport pathways, and active ion concentration. The results show that with increase in the fraction of ceramic LiLaZrO (LLZO) phase in the LLZO-poly(ethylene oxide) composites, ion mobility decreases, ion transport pathways transit from polymer to ceramic routes, and the active ion concentration increases. These changes in ion mobility, transport pathways, and concentration collectively explain the observed trend of ionic conductivity in composite electrolytes. Liquid additives alter ion transport pathways and increase ion mobility, thus enhancing ionic conductivity significantly. It is also found that a higher content of LLZO leads to improved electrochemical stability of composite electrolytes. This study provides insight into the recurring observations of compositional dependence of ionic conductivity in current composite electrolytes and pinpoints the intrinsic limitations of composite electrolytes in achieving fast ion conduction.
Polymer-ceramic composite electrolytes are emerging as a promising solution to deliver high ionic conductivity, optimal mechanical properties, and good safety for developing high-performance all-solid-state rechargeable batteries. Composite electrolytes have been prepared with cubic-phase Li7 La3 Zr2 O12 (LLZO) garnet and polyethylene oxide (PEO) and employed in symmetric lithium battery cells. By combining selective isotope labeling and high-resolution solid-state Li NMR, we are able to track Li ion pathways within LLZO-PEO composite electrolytes by monitoring the replacement of (7) Li in the composite electrolyte by (6) Li from the (6) Li metal electrodes during battery cycling. We have provided the first experimental evidence to show that Li ions favor the pathway through the LLZO ceramic phase instead of the PEO-LLZO interface or PEO. This approach can be widely applied to study ion pathways in ionic conductors and to provide useful insights for developing composite materials for energy storage and harvesting.
Composite polymer solid electrolytes (CPEs) containing ceramic fillers embedded inside a polymer-salt matrix show great improvements in Li ionic conductivity compared to the polymer electrolyte alone. Lithium lanthanum zirconate (LiLaZrO, LLZO) with a garnet-type crystal structure is a promising solid Li conductor. We show that by incorporating only 5 wt % of the ceramic filler comprising undoped, cubic-phase LLZO nanowires prepared by electrospinning, the room temperature ionic conductivity of a polyacrylonitrile-LiClO-based composite is increased 3 orders of magnitude to 1.31 × 10 S/cm. Al-doped and Ta-doped LLZO nanowires are also synthesized and utilized as fillers, but the conductivity enhancement is similar as for the undoped LLZO nanowires. Solid-state nuclear magnetic resonance (NMR) studies show that LLZO NWs partially modify the PAN polymer matrix and create preferential pathways for Li conduction through the modified polymer regions. CPEs with LLZO nanoparticles and AlO nanowire fillers are also studied to elucidate the role of filler type (active vs passive), LLZO composition (undoped vs doped), and morphology (nanowire vs nanoparticle) on the CPE conductivity. It is demonstrated that both intrinsic Li conductivity and nanowire morphology are needed for optimal performance when using 5 wt % of the ceramic filler in the CPE.
While solid-state batteries are tantalizing for achieving improved safety and higher energy density, solid ion conductors currently available fail to satisfy the rigorous requirements for battery electrolytes and electrodes. Inorganic ion conductors allow fast ion transport, but their rigid and brittle nature prevents good interfacial contact and impedes device integration and stability.Conversely, flexible polymeric ion conductors provide better interfacial compatibility and mechanical tolerance, but suffer from inferior ionic conductivity (< 10 −5 S cm −1 at room temperature) due to the coupling of ion transport with the polymer chain motion 1-3 . In this work, we report a general design strategy for achieving one-dimensional (1D), high-performance polymer solid-state ion conductors through molecular channel engineering, which we demonstrate via Cu 2+ -coordination of cellulose nanofibrils. The cellulose nanofibrils by themselves are not ionic conductive; however, by opening the molecular channels between the cellulose chains through Cu 2+ coordination we are able to achieve a Li-ion conductivity as high as 1.5×10 −3 S cm −1 at room temperature-a record among all known polymer ion conductors. This improved conductivity is enabled by a unique Li + hopping mechanism that is decoupled from the polymer segmental motion. Also benefitted from such decoupling, the cellulose-based ion conductor demonstrates multiple advantages, including a high transference number (0.78 vs. 0.2-0.5 in other polymers 2 ), low activation energy (0.19 eV), and a wide electrochemical stability window (4.5 V) that accommodate both Li metal anode and high-voltage cathodes. Furthermore, we demonstrate this 1D ion conductor not only as a thin, high-conductivity solid-state electrolyte but also as an effective ion-conducting additive for the solid cathode, providing continuous ion transport pathways with a low percolation threshold, which allowed us to utilize the thickest LiFePO4 solidstate cathode ever reported for high energy density. This approach has been validated with other 3 polymers and cations (e.g., Na + and Zn 2+ ) with record-high conductivities, offering a universal strategy for fast single-ion transport in polymer matrices, with significance that could go far beyond safe, high-performance solid-state batteries.
Nanotechnology plays a significant role in drug development. As carriers, polymeric nanoparticles can deliver vaccine antigens, proteins, and drugs to the desired site of action. Polymeric nanoparticles with lower cytotoxicity can protect the delivered antigens or drugs from degradation under unfavorable conditions via a mucosal administration route; further, the uptake of nanoparticles by antigen-presenting cells can increase and induce potent immune responses. Additionally, nanomaterials are widely used in vaccine delivery systems because nanomaterials can make the vaccine antigen long-acting. This review focuses on some biodegradable polymer materials such as natural polymeric nanomaterials, chemically synthesized polymer materials, and biosynthesized polymeric materials, and points out the advantages and the direction of research on degradable polymeric materials. The application and future perspectives of polymeric materials as delivery carriers and vaccine adjuvants in the field of drugs and vaccines are presented. With the increase of knowledge and fundamental understandings of polymer-based nanomaterials, means of integrating some other attractive properties, such as slow release, target delivery, and alternative administration methods and delivery pathways are feasible. Polymer-based nanomaterials have great potential for the development of novel vaccines and drug systems for certain needs, including single-dose and needle-free deliveries of vaccine antigens and drugs in the future.
Organic−inorganic hybrid solid electrolytes are expected to integrate the merits of both moieties for addressing the challenges in achieving fast ion conduction and high stability for energy storage applications. Li 10 GeP 2 S 12 (LGPS)-poly-(ethylene oxide) (PEO) (bis(trifluoromethane)sulfonimide lithium (LiTFSI)) hybrid electrolytes have been prepared, which exhibit ionic conductivities up to 0.22 mS cm −1 and good longterm cycling stability against Li-metal. High-resolution solid-state 6 Li NMR is employed to examine the local structural environments of Li ions in the LGPS-PEO (LiTFSI) hybrids, which identifies Li ions from PEO (LiTFSI), in bulk LGPS, and at LGPS-PEO interfaces. Tracer-exchange Li NMR reveals that Li ions transport mainly through LGPS-PEO interfaces. The impact of LGPS and LiTFSI contents on the interface chemistry within LGPS-PEO hybrid electrolytes has been examined. The measured conductivities of LGPS-PEO hybrids positively correlate with the available Li ions at LGPS-PEO interfaces. This study provides insights for engineering interfaces in organic− inorganic hybrids to develop high-performance electrolytes for solid-state rechargeable batteries.
It is determined with isotope-replacement NMR that Li ions transport via TEGDME-containing phases in a representative composite electrolyte LLZO–PEO–TEGDME.
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