Self-assembly synthesis of solid polymer electrolyte with carbonate terminated poly (ethylene glycol) matrix and its application for solid state lithium battery

A facile one-pot synthesis of solid polymer electrolytes(SPEs), composed of carbonate terminated poly(ethylene glycol)(CH3O-PEG-IC), poly(ethylene glycol)-block-polystyrene(PEG-b-PS) block copolymer nanoparticles containing a conductive PEG corona, fumed SiO2 and Li TFSI salt via polymerization-induced self-assembly is proposed. This method to prepare SPEs has the advantages of one-pot convenient synthesis, avoiding use of organic solvent and conveniently adding inorganic additives. CH3O-PEG-IC combines advantages of PEG and polycarbonate, the in situ synthesized PEG-b-PS nanoparticles containing a rigid polystyrene(PS) core and a PEG corona guarantee continuous lithium ion transport in the synthesized SPEs, and the fumed SiO2 optimizes the interfacial properties and improves the electrochemical stability, all of which afford SPEs a well considerable room temperature ionic conductivity of 1.73 × 10^-4S/cm, high lithium transference number of 0.53, and wide electrochemical stability window of 5.5 V(vs. Li^+/Li). By employing these SPEs, the assembled solid state cells of Li FePO4 |SPEs|Li exhibit considerable cell performance.

Thermoreversible Thickening and Self-assembly Behaviors of pH/Temperature Dually Responsive Microgels with Interpenetrating Polymer Network Structure

The pH /temperature dually responsive microgels of interpenetrating polymer network( IPN) structure composed of poly( N-isopropylacrylamide)( PNIPAM) network and poly( acrylic acid)( PAA) network( PNIPAM /PAA IPN microgels) were synthesized by seed emulsion polymerization. The results obtained by dynamic laser light scattering( DLLS) show that the microgels have good pH /temperature dual sensitivities. The temperature sensitive component and the pH sensitive component inside the microgels have little interference with each other. The rheological properties of the concentrated PNIPAM /PAA IPN microgel dispersions as a function of temperature at pH 4. 0 or 7. 0 were investigated by viscometer,and the results displayed that only at pH 7. 0 the dispersions presented thermoreversible thickening behavior. Then the PNIPAM /PAA fibers were prepared by self-assembly of the PNIPAM /PAA IPN microgels in the ice-crystal templates formed by unidirectional liquid nitrogen freezing method. Field emission scanning electron microscopy( FESEM) images indicate that the PNIPAM /PAA fibers are rounded,randomly orientated and interweaved.

Electropolymerization of 4-Aminothiophenol Self-AssembledMonolayer on Au Electrode

In this letter. we report that oxidation of 4-aminothiophenol self-assembled monolayeron An electrode produces a couple of redox current peaks with close peak potentials in 0.5 mol/LHCIO4 aqueous solution, and the peaks are ascribed to an electroactive monolayer.Electrochemical properties of the monolayer polymer were investigated with use ofelectrochemical quartz crystal microbalance and cyclic voltammetry.

Self-assembled monolayer modified copper(Ⅰ) iodide hole transport layer for efficient polymer solar cells

The morphology of the copper iodide （CuI） film as an inorganic p-type material has an important influence on enhancing the performance of polymer solar cells （PSCs）. A self-assembled monolayer of 3-aminopropanoic acid （C3-SAM） was used on the surface of indium tin oxide （ITO） before depositing the CuI films. Consequently, a well-distributed and smooth CuI film was formed with pinhole free and complete surface coverage. The root mean square of the corresponding CuI film was reduced from 3.63 nm for ITO/CuI to 0.77 nm. As a result, the average power conversion efficiency （PCE） of PSCs with the device structure of ITO/C3-SAM/CuI/P3HT：PC61BM/ZnO/Al increased significantly from 2.55% （best 2.66%） to 3.04% （best 3.20%） after C3-SAM treatment. This work provides an effective strategy to control the morphology of CuI films through interracial modification and promotes its application in efficient PSCs.

Study on durability of Pt supported on graphitized carbon under simulated start-up/shut-down conditions for polymer electrolyte membrane fuel cells

The primary issue for the commercialization of proton exchange membrane fuel cell（PEMFC） is the carbon corrosion of support under start-up/shut-down conditions. In this study, we employ the nanostructured graphitized carbon induced by heat-treatment. The degree of graphitization starts to increase between 900 and 1300 ℃ as evidenced by the change of specific surface area, interlayer spacing, and ID/IG value. Pt nanoparticles are deposited on fresh carbon black（Pt/CB） and carbon heat-treated at 1700 ℃（Pt/HCB17） with similar particle size and distribution. Electrochemical characterization demonstrates that the Pt/HCB17 shows higher activity than the Pt/CB due to the inefficient microporous structure of amorphous carbon for the oxygen reduction reaction. An accelerating potential cycle between 1.0 and 1.5 V for the carbon corrosion is applied to examine durability at a single cell under the practical start-up/shutdown conditions. The Pt/HCB17 catalyst shows remarkable durability after 3000 potential cycles. The Pt/HCB17 catalyst exhibits a peak power density gain of 3%, while the Pt/CB catalyst shows 65% loss of the initial peak power density. As well, electrochemical surface area and mass activity of Pt/HCB17 catalyst are even more stable than those of the Pt/CB catalyst. Consequently, the high degree of graphitization is essential for the durability of fuel cells in practical start-up/shut-down conditions due to enhancing the strong interaction of Pt and π-bonds in graphitized carbon.

Hollow Bio-derived Polymer Nanospheres with Ordered Mesopores for Sodium-Ion Battery

Bio-inspired hierarchical self-assembly provides elegant and powerful bottom-up strategies for the creation of complex materials.However,the current self-assembly approaches for natural bio-compounds often result in materials with limited diversity and complexity in architecture as well as microstructure.Here,we develop a novel coordination polymerization-driven hierarchical assembly of micelle strategy,using phytic acid-based natural compounds as an example,for the spatially controlled fabrication of metal coordination bio-derived polymers.The resultant ferric phytate polymer nanospheres feature hollow architecture,ordered meso-channels of^12 nm,high surface area of 401 m2 g−1,and large pore volume of 0.53 cm3 g−1.As an advanced anode material,this bio-derivative polymer delivers a remarkable reversible capacity of 540 mAh g−1 at 50 mA g−1,good rate capability,and cycling stability for sodium-ion batteries.This study holds great potential of the design of new complex bio-materials with supramolecular chemistry.

Nanofabrication in Polymer Solutions

This review covers recent advances in fabrication of nanomaterials in polymer solutions with emphasis on using the self assembled amphiphilic block copolymers in solution to fabricate organic/inorganic composites with nanoscale modifications. The phase behavior of block copolymers in water and the use of templates to form ordered nanostructures are reviewed in detail. Modern physical techniques for nanoscale characterization are also introduced. The authors suggested that this approach should provide new routes to create materials with interesting morphologies for many different applications.

NOVEL SYNTHESIS OF LONG MULTI-BLOCK HETEROPOLYMER CHAINS WITH AN ORDERED SEQUENCE AND CONTROLLABLE BLOCK LENGTHS

It had very long been a dream in polymer science to synthesize long multi-block polymer chains with an orderedchain sequence and controllable block lengths. Using ionic or living free radical polymerization or furnishing each end ofpolymer blocks with a reactive functional group, one can only prepare heteropolymer chains with few long blocks, such asdiblock and triblock copolymers. The most plausible result so far was a pentablock copolymer. Recently, using a combinationof polymer physics and synthetic chemistry, we have invented self-assembly assisted polycondensation (SAAP). Thiscommunication reports the results of using this novel. method to connect 10-100 triblock polymer chains together to formlong multi-block heteropolymer chains with an ordered sequence and controllable block lengths.

Assembly of CdS Nanowires from Solution Using Oriented Nanofibers

This paper presents an universal assembly approach,based on the oriented nanofibers,for the formation of large-scale ordered nanowire arrays.First,CdS NWs solution is dripped onto the substrate surface.Second,before the CdS NWs solution evaporates,the oriented nanofibers slides along the substrate surface to assemble the CdS nanowires.The mechanism involving ordered alignment of nanowires on the substrate surface was investigated based on our experimental results.The resulting nanowires arrays can be further used for the creation of massive nanoelectronic-device arrays.

Novel phosphonated polymer without anhydride formation for proton exchange membrane fuel cells

Proton exchange membrane fuel cells(PEMFCs)are regarded as one of the most promising clean energy technology because of their high energy density,silent emission-free operation,and wide applications[1].Recently,anion exchange membrane fuel cells(AEMFCs)has emerged as an alternative to PEMFCs.

Blood Compatibility of Amphiphilic Poly(N-α-acrylamide-L-lysine-<i>b</i>-dimethylsiloxane) Block Copolymers

Amphiphilic block copolymers poly(LysAA-b-DMS) consisting of a hydrophilic poly(N-α-acrylamide-L-lysine) [poly(LysAA)] segment with different molecular weights and a hydrophobic polydimethylsiloxane (PDMS) segment were prepared as follows. The precursor copolymer poly(Boc-LysAA-OtBu-b-PDMS) was obtained from radical polymerization of N-α-acrylamide-N-ε-tert-butoxycarbonyl-L-lysine-tert-butylester (Boc-LysAA-OtBu) initiated with 4,4’-azobis(polydimethylsiloxane 4-cyanopentanoate) (azo-PDMS) with the molecular weight of PDMS Mw = 4.3 × 103 in the presence of 2-mercaptoethanol (2-ME) as a chain-transfer agent. Removal of the protecting groups of the precursor copolymer was carried out in 80% trifluoroacetic acid aqueous solution to give poly(LysAA-b-DMS)-1-3. The weight average molecular weight of poly(LysAA-b-DMS)-1-3 was Mw = 1.02 × 104 – 2.52 × 104. From the 1H-NMR and fluorescence spectra measurements, poly(LysAA-b-DMS)-1-3 was determined to self-organize and form core-shell micelles in water. The critical micelle concentration (CMC) increased to 1000 - 4000 mg·L–1 with increasing molar ratio of the poly(LysAA) segment from 0.42 to 0.65. From morphological analysis with a scanning probe microscope (SPM), poly(LysAA-b-DMS) has microphase-separated structures made up of hydrophilic and hydrophobic regions with the domain size ranging from several tens to several hundreds of nanometers. Inhibition of thrombin activity of poly(LysAA-b-DMS) was evaluated from the Michaelis constant (KM) and catalytic activity (kcat) for the enzymatic reaction of thrombin and synthetic substrate S-2238 in the presence of poly(LysAA-b-DMS). The KM and kcat were 0.10 - 0.11 mM and 4.04 × 105 – 4.26 × 105 min–1, respectively. Fibrinolytic activity was also verified from the transformation of plasminogen to plasmin by tissue plasminogen activator (t-PA) using synthetic substrate S-2251 in the presence of poly(LysAA-b-DMS). The KM and kcat were 0.07 mM and 5.73 × 106 –5.95 × 106 min–1, respectively.

A NEW STRATEGY FOR THE DESIGN OF LIQUID CRYSTALLINE POLYMERS WITH FLEXIBLE AND APOLAR BUILDING BLOCKS

The synthesis and characterization of a new series of liquid crystalline polymers, poly(dicycloalkylvinylterephthalate)s, are reported. The basic building blocks of these polymers are not mesogenic by themselves. However,very stable mesophases can be generated by self-assembly of the polymer molecules. This approach suggests a novel designstrategy of liquid crystalline polymers with flexible and apolar building blocks.

Polymer Coatings for Protection of Wood and Wood-Based Materials

Three major types of protective coating of wood and wood-based materials have been considered. These three types include the coatings based on carboxyl-containing water-soluble polymers which are easily cross-linked by inorganic salts or OH-containing compounds, pH-sensitive coatings and polymer multi-layer structures. First of three mentioned approaches allows affecting permeability and enhancing the prevention the loss of water from the surface of wood to its surrounding. The advantage of the second approach is its ability to vary and purposely adjust the polymer composition and the number and distribution of -COOH groups in the chain which make the originally water-soluble polymers completely insoluble. The strong feature of the third approach which includes broad use of hydrogen-bonded films produced by layer-by-layer self-assembly is the possibility of manipulation of coatings stability after construction.

A TEMPERATURE AND pH DOUBLE SENSITIVE CHOLESTERIC POLYMER FILM FROM A PHOTOPOLYMERIZABLE CHIRAL HYDROGEN-BONDED ASSEMBLY

In this study, a novel H-bonded cholesteric polymer film responding to temperature and pH by changing the reflection color was fabricated. The H-bonded cholesteric polymer film was achieved by UV-photopolymerizing a cholesteric liquid crystal （Ch-LC） monomers mixture containing a photopolymerizable chiral H-bonded assembly （PCHA）. The cholesteric polymer film based on PCHA can be thermally switched to reflect red color from the initial green/yellow color as temperature is increased, which is due to a change in helical pitch induced by the weakening of H-bonded interaction in the polymer film. Additionally, the selective reflection band （SRB） of the cholesteric polymer film in solution with pH 〉 7 showed an obvious red shift with increasing pH values. While the SRB of the cholesteric polymer film in solutions with pH = 7 and pH 〈 7 hardly changed. This pH sensitivity in solutions with pH 〉 7 could be explained by the breakage of H-bonds in the cholesteric polymer film and the structure changes induced by --OH- and --K＋ ions in the alkaline solution. In contrast, it couldn＇t happen in the neutral and acidic solutions. The cholesteric polymer film in this study can be used as optical/photonic papers, optical sensors and LCs displays, etc.

Self-assembly as a route to one-dimensional lanthanum(Ⅲ) salicylaldimine coordination polymer

The self-assembled formation of a one-dimensional lanthanum salicylald imine coordination polymer was proved by the X-ray diffraction analysis of new l anthanum(Ⅲ) nitrate complex containing N,N’-bis(salicylidene)-1,5-pentanediami ne ligand(H2L) . It was obtained in situ in a one-step,metal-templated condensa tion of salicylaldehyde with 1,5-pentanediamine(cadaverine,biogenic polyamine) and characterized by microanalysis and spectroscopic(IR,ESI-MS,UV-Vis,and 1 H NMR) data. The [La(NO3) 3(μ-H2L) 2]∞ complex displayed 10-coordinate distorted bicapped dodecahedron geometry with unusual coordination pattern of undeprotonat ed salicylaldimines which acted as μ-bridging ditopic ligands using exclusivel y the oxygens as donor atoms with the nitrogen atoms not being involved in the c oordination environment.

Polymersomes:From Macromolecular Self-Assembly to Particle Assembly

What is the most favorite and original chemistry developed in your research group?Ring-opening polymerization-induced self-assembly of N-carboxyanhydrides(NCA-PISA),and fusion-induced particle assembly(FIPA).How do you get into this specific field?Could you please share some experiences with our readers?NCA-PISA was developed to solve the biodegradability problem of nanoparticles by traditional PISA,while FIPA was inspired by nature.

Engineering membrane electrode assembly for advanced polymer electrolyte water electrolyzer

As an important energy carrier in terms of carbon neutrality,green hydrogen produced by water electrolysis using renewable electricity has attracted worldwide attention.The polymer electrolyte water electrolyzer(PEWE)has the potential to be a mainstay in the green hydrogen market in the future because of its superior performance.However,the development of PEWE is constrained by the slow progress of the membrane electrode assembly(MEA),which is an essential component of PEWE and largely determines the cost and performance of the system.Therefore,the MEA must be optimized from the aspects of reducing cost and improving performance to promote the development of PEWEs.In this review,we first discuss the recent progress of the materials and design strategies of MEA,including the cost,activity,and stability of catalysts,distribution and thickness of ionomers,and ion transport efficiency of ion exchange membranes(IEMs).Then,the effects of all components and interlayer interfaces on the ions,electrons,and mass transfer in MEA and,consequently,the performance of PEWE are analyzed.Finally,we propose perspectives on developing MEA by optimizing the catalyst activity and stability of IEM,interface contact between adjacent components,and evaluation methods of performance.

Controlled Self-assembly of Thermo-responsive Amphiphilic H-shaped Polymer for Adjustable Drug Release

Despite the fact that some progress has been made in the self-assembly of H-shaped polymers, the corresponding self-assemblies that respond to external stimulus and are further utilized to adjust the release of drugs are still deficient. The stimuli-responsive segments with amphiphilic H-shaped structure are generally expected to enhance the controllability of self-assembly process. The synthesis and self-assembly behavior of thermo-responsive amphiphilic H-shaped polymers with poly（ethylene glycol） （PEG）, polytetrahydrofuran （PTHF） and poly（N-isopropyl acrylamide） （PNIPAM） as building blocks are reported in this paper. The inner architecture structure and size of complex micelles formed by H-shaped self-assemblies were effectively adjusted when the solution temperature was increased above the lower critical solution temperature of PNIPAM segments. Furthermore, it was found that the architecture of self-assemblies underwent a transition from the complex micelles based on primary micelles with hybrid PEG/PNIPAM shells to large complex micelles based on primary micelles with hybrid PTHF/PNIPAM cores and PEG shells during the thermal-induced self-assembly process. The adjustable release rate ofdoxorubicin （DOX） from the DOX-loaded complex micelles and basic cell experiments further proved the feasibility of these self-assemblies as the thermal-responsive drug delivery system.

Supramolecular self-assembly and controllable drug release of thermosensitive hyperbranched multiarm copolymers

A novel temperature-responsive hyperbranched multiarm copolymer with a hydrophobic hyperbranched poly(3-ethyl-3-(hydroxymethyl)oxetane)(HBPO) core and thermosensitive poly(N-isopropylacrylamide)(PNIPAM) arms was synthesized via the atom transfer radical polymerization(ATRP) of NIPAM monomers from a hyperbranched HBPO macroinitiator.It was found that HBPO-star-PNIPAM self-assembled into multimolecular micelles(around 60 nm) in water at room temperature according to pyrene probe fluorescence spectrometry,1H NMR,TEM,and DLS measurements.The micelle solution showed a reversible thermosensitive phase transition at a lower critical solution temperature(LCST)(around 32°C) observed by variable temperature optical absorbance measurements.Variable temperature NMR and DLS analyses demonstrated that the LCST transition originated from the secondary aggregation of the micelles driven by increasing hydrophobic interaction due to the dehydration of PNIPAM shells upon heating.The drug loading and release properties of HBPO-star-PNIPAM micelles were also investigated using prednisone acetate as a model drug.The micelles showed a much improved drug encapsulation efficiency and temperature-dependent sustainable release behavior due to the special micellar structure.The micelles exhibited no apparent cytotoxicity against human HeLa cells.