Synthesis and Characterization of Gel Polymer Electrolyte Based on Epoxy Group via Cationic Ring-Open Polymerization for Lithium-Ion Battery.

The polymer electrolytes are considered to be an alternative to liquid electrolytes for lithium-ion batteries because of their high thermal stability, flexibility, and wide applications. However, the polymer electrolytes have low ionic conductivity at room temperature due to the interfacial contact issue and the growing of lithium dendrites between the electrolytes/electrodes. In this study, we prepared gel polymer electrolytes (GPEs) through an in situ thermal-induced cationic ring-opening strategy, using LiFSI as an initiator. As-synthesized GPEs were characterized with a series of technologies. The as-synthesized PNDGE 1.5 presented good thermal stability (up to 150 °C), low glass transition temperature (Tg < −40 °C), high ionic conductivity (>10−4 S/cm), and good interfacial contact with the cell components and comparable anodic oxidation voltage (4.0 V). In addition, PNGDE 1.5 exhibited a discharge capacity of 131 mAh/g after 50 cycles at 0.2 C and had a 92% level of coulombic efficiency. Herein, these results can contribute to developing of new polymer electrolytes and offer the possibility of good compatibility through the in situ technique for Li-ion batteries.

UV-Cured Cross-Linked Astounding Conductive Polymer Electrolyte for Safe and High-Performance Li-Ion Batteries.

UV-cured cross-linked polymer electrolytes are promising electrolytes for safe Li-ion batteries (LIBs) application due to their excellent conduction ability, low glass-transition temperature (Tg), and high discharge capacity. Herein, we have prepared novel fluorosulfonylimide methacrylic-based cross-linked polymer electrolyte membranes for LIBs via UV-curing process, which is a well-known, easy, low-cost, fast, and reliable technique. The synthesized UV-reactive novel methacrylate monomer with directly attached fluorosulfonylimide functional group methacryloylcarbamoyl sulfamoyl fluoride (MACSF) was used as a precursor for UV curing along with poly(ethylene glycol) dimethacrylate (PEGDMA) and lithium bis(fluorosulfonyl)imide (LiFSI). The results demonstrated that the cross-linked membrane with an optimized amount (30 wt %) of MACSF monomer (noted as CPE-3) showed the best performance. The nonflammable fluorosulfonyl group (a hydrophilic group of MACSF monomer) in the polymer matrix formed a wide channel, as a result of which Li ion can migrate easily via forming an ionic linkage. The CPE-3 electrolyte exhibited a low Tg (-79 °C), excellent phase separation, high conductivity (σ) (ca. 3.5 × 10-4 and 8.50 × 10-3 S·cm-1 at 30 and 80 °C, respectively), and high flame retardancy. The battery performance of half-cell (LiFePO4/CPE-3/Li) and full cell (LiFePO4/CPE-3/graphite) with CPE-3 electrolyte were attractive: discharge capacities (155 and 152 mAh/g) with the capacity retentions of 96.17 and 95.17% after 500 cycles at 0.1 C rate for half-cell and full-cell LIBs, respectively.

Branched Sulfonimide-Based Proton Exchange Polymer Membranes from Poly(Phenylenebenzopheneone)s for Fuel Cell Applications.

Improved proton conductivity and high durability are now a high concern for proton exchange membranes (PEMs). Therefore, highly proton conductive PEMs have been synthesized from branched sulfonimide-based poly(phenylenebenzophenone) (SI-branched PPBP) with excellent thermal and chemical stability. The branched polyphenylene-based carbon-carbon backbones of the SI-branched PPBP membranes were attained from the 1,4-dichloro-2,5-diphenylenebenzophenone (PBP) monomer using 1,3,5-trichlorobenzene as a branching agent (0.1%) via the Ni-Zn catalyzed C-C coupling reaction. The as-synthesized SI-branched PPBP membranes showed 1.00~1.86 meq./g ion exchange capacity (IEC) with unique dimensional stability. The sulfonimide groups of the SI-branched PPBP membranes had improved proton conductivity (75.9-121.88 mS/cm) compared to Nafion 117 (84.74 mS/cm). Oxidation stability by thermogravimetric analysis (TGA) and Fenton's test study confirmed the significant properties of the SI-branched PPBP membranes. Additionally, a very distinct microphase separation between the hydrophobic and hydrophilic moieties was observed using atomic force microscopic (AFM) analysis. The properties of the synthesized SI-branched PPBP membranes demonstrate their viability as an alternative PEM material.

Highly Proton Conductive Sulfonyl Imide Based Polymer Blended from Poly(arylene ether sulfone) and Parmax-1200 for Fuel Cells.

Thermally and chemically stable, sulfonyl imide-based polymer blends have been prepared from sulfonimide poly(arylene ether sulfone) (SI-PAES) and sulfonimide Parmax-1200 (SI-Parmax-1200) using the solvent casting method. Initially, sulfonimide poly(arylene ether sulfone) (SI-PAES) polymers have typically been synthesized via direct polymerization of bis(4-chlorophenyl) sulfonyl imide (SI-DCDPS) and bis(4-fluorophenyl) sulfone (DFDPS) with bisphenol A (BPA). Subsequently, SI-Parmax-1200 has been synthesized via post-modification of the existing Parmax-1200 polymer followed by sulfonation and imidization. The SI-PAES/SI-Parmax-1200 blend membranes show high ion exchange capacity ranging from 1.65 to 1.97 meq/g, water uptake ranging from 22.8 to 65.4% and proton conductivity from 25.9 to 78.5 mS/cm. Markedly, the SI-PAES-40/SI-Parmax-1200 membrane (blended-40) exhibits the highest proton conductivity (78.5 mS/cm), which is almost similar to Nafion 117® (84.73 mS/cm). The thermogravimetric analysis (TGA) and Fenton's test confirm the excellent thermal and chemical stability of the synthetic polymer blends. Furthermore, the scanning electron microscopy (SEM) study shows a distinct phase separation at the hydrophobic/hydrophilic segments, which facilitate proton conduction throughout the ionic channel of the blend polymers. Therefore, the synthetic polymer blends represent an alternative to Nafion 117® as proton exchangers for fuel cells.

Sulfonyl Imide Acid-Functionalized Membranes via Ni (0) Catalyzed Carbon-Carbon Coupling Polymerization for Fuel Cells.

Polymer membranes, having improved conductivity with enhanced thermal and chemical stability, are desirable for proton exchange membranes fuel cell application. Hence, poly(benzophenone)s membranes (SI-PBP) containing super gas-phase acidic sulfonyl imide groups have been prepared from 2,5-dichlorobenzophenone (DCBP) monomer by C-C coupling polymerization using Ni (0) catalyst. The entirely aromatic C-C coupled polymer backbones of the SI-PBP membranes provide exceptional dimensional stability with rational ion exchange capacity (IEC) from 1.85 to 2.30 mS/cm. The as-synthesized SI-PBP membranes provide enhanced proton conductivity (107.07 mS/cm) compared to Nafion 211® (104.5 mS/cm). The notable thermal and chemical stability of the SI-PBP membranes have been assessed by the thermogravimetric analysis (TGA) and Fenton's test, respectively. The well distinct surface morphology of the SI-PBP membranes has been confirmed by the atomic force microscopy (AFM). These results of SI-PBP membranes comply with all the requirements for fuel cell applications.

A two-step approach for improved exfoliation and cutting of boron nitride into boron nitride nanodisks with covalent functionalizations.

The synthesis of boron nitride nanodisks (BNNDs) with reducing the size and having fewer disk layers, and low optical band gap (E g) is essential for practical applications in electronics and optoelectronic devices. So far, the large-scale preparation of hydroxyl (-OH) and hydroperoxyl (-OOH) functionalized boron nitride nanosheets and BNNDs with reduced E g is still a challenge. This research demonstrates the scalable and solution process synthesis of hydroxyl (-OH) and hydroperoxyl (-OOH) functionalization of BNNDs at the edges and basal planes from pristine hexagonal boron nitride (h-BN) by the combination of modified Hummer's method and Fenton's chemistry. Modified Hummer's method induces exfoliation and cutting of the h-BN into BNNDs with a low percentage of -OH functionalization (6.90%), which is further exfoliated and cut by Fenton's reagent with improved -OH and -OOH functionalization (ca. 17.25%). The combination of these two methods allows us to reduce the size of the OH/OOH-BNNDs to ca. 200 nm with the number of disk layers in the range from ca. 6-11. Concurrently, the E g of h-BN was decreased from ca. 5.10 to ca. 3.58 eV for OH/OOH-BNNDs, which enables the possible application of OH/OOH-BNNDs in semiconductor electronics. The high percentage of -OH and -OOH functionalizations in the OH/OOH-BNNDs enablesg them to disperse in various solvents with high long-term stability.

Highly Conductive and Flexible Gel Polymer Electrolyte with Bis(Fluorosulfonyl)imide Lithium Salt via UV Curing for Li-Ion Batteries.

A series of new self-standing gel polymer electrolytes (SGPEs) were fabricated by ultraviolet (UV) curing and investigated for application in flexible lithium-ion batteries. Compared with traditional gel polymer electrolytes (combine with solvents or plasticizers), these new SGPEs were prepared simply by curing different weight ratios of lithium bis(fluorosulfonyl)imide (LiFSI) with a methacrylic linear monomer, poly (ethylene glycol) dimethacrylate (PEGDMA). Noticeably, there were no solvents or plasticizers combined with the final SGPEs. Owing to this, the SGPEs showed high flexibility and strong mechanical stability. Some paramount physicochemical and electrochemical characters were observed. The SGPEs demonstrated good thermal stability below 150 °C and an extremely low glass transition temperature (Tg) (around -75 °C). Moreover, plastic crystal behaviors were also identified in this study. Ultimately, the SGPEs demonstrated excellent ionic conductivity at room temperature, which proves that these new SGPEs could be widely applied as a prospective electrolyte in flexible lithium-ion batteries.

Remarkable Conductivity of a Self-Healing Single-Ion Conducting Polymer Electrolyte, Poly(ethylene-co-acrylic lithium (fluoro sulfonyl)imide), for All-Solid-State Li-Ion Batteries.

Single-ion conducting polymer electrolyte (SICPE) is a safer alternative to the conventional high-performance liquid electrolyte for Li-ion batteries. The performance of SICPEs-based Li-ion batteries is limited due to the low Li+ conductivities of SICPEs at room temperature. Herein, we demonstrated the synthesis of a novel SICPE, poly(ethylene-co-acrylic lithium (fluoro sulfonyl)imide) (PEALiFSI), with acrylic (fluoro sulfonyl)imide anion (AFSI). The solvent- and plasticizer-free PEALiFSI electrolyte, which was assembled at 90 °C under pressure, exhibited self-healing properties with remarkably high Li+ conductivity (5.84 × 10-4 S cm-1 at 25 °C). This is mainly due to the self-healing behavior of this electrolyte, which induced to increase the proportion of the amorphous phase. Additionally, the weak interaction of Li+ with the resonance-stabilized AFSI anion is also responsible for high Li+ conductivity. This self-healed SICPE showed high Li+ transference number (ca. 0.91), flame and heat retardancy, and good thermal stability, which concurrently delivered ca. 88.25% (150 mAh g-1 at 0.1C) of the theoretical capacitance of LiFePO4 cathode material at 25 °C with the full-cell configuration of LiFePO4/PEALiFSI/graphite. Furthermore, the self-healed PEALiFSI-based all-solid-state Li battery showed high electrochemical cycling stability with the capacity retention of 95% after 500 charge-discharge cycles.

Simple, low-cost, sensitive and label-free aptasensor for the detection of cardiac troponin I based on a gold nanoparticles modified titanium foil.

This research demonstrated the electrochemical modification of low-cost titanium (Ti) metal substrate with gold nanoparticles (AuNPs) for the aptamer-based detection of cardiac troponin I (cTnI). AuNPs were deposited onto Ti sheets by the potential-step deposition method with high density and homogeneity as well as good crystallinity. It was then applied as a transducer to immobilize a thiol-functionalized DNA aptamer via the self-assembled monolayer mechanism for the specific binding of cTnI. This was verified through electrochemical and morphological analyses. The aptasensor could detect cTnI in a linear range of 1-1100 pM with a detection limit of ca. 0.18 pM. The aptasensor showed high sensitivity and specificity to cTnI over other interfering compounds with good recoveries in the diluted human serum samples.

Synthesis of Sulfonation Poly(N-propylsulfonicacid isatin biphenylene) for Polymer Electrolyte Membrane Fuel Cell Containing SiO2 Nanocomposite Membrane.

Polymer containing isatin was synthesized by super acid-catalyzed carbon-carbon coupling reaction. Propylsulfonic acid was grafted on isatin unit by substitution reaction with potassium salt of 3-bromo-1-propanesulfonic acid. The sulfonic acid composition was regulated at 25~80 mol% of propylsulfonic acid in order to achieve expected ion exchange capacity of maximum 2.0 meq/g. The copolymers were of high molecular weight (inherent viscosity, ηinh = 1.2 dL/g) to afford a tough membrane by solution casting. Composite membranes were prepared by sulfonated polymer and SiO2 nanoparticles (20 nm, 4~10% wt). All these composite membranes were casted from the solution of sulfonated polymer in dimethylsulfoxide (DMSO) to afford 25 µm. The structural properties of the synthesized polymers were investigated by 1H NMR spectroscopy. The membranes were studied by ion exchange capacity (IEC), water uptake, dimensional stability and proton conductivity assessment by comparing with Nafion®. As increasing the IEC values, the small hydrophobic components induced high proton conductivities and proton diffusion coefficients. These kinds of membranes without ether linkages showed low water swelling as well.

A glassy carbon electrode modified with poly(2,4-dinitrophenylhydrazine) for simultaneous detection of dihydroxybenzene isomers.

2,4-Dinitrophenylhydrazine (DNPH) was electropolymerized on the surface of an anodized glassy carbon electrode by cyclic voltammetry. The anodized electrode has a highly electroactive surface due to the creation of chemically functionalized graphitic nanoparticles, and this facilitates the formation of poly-DNPH via radical polymerization. Poly-DNPH displays excellent redox activity due to the presence of nitro groups on its backbone. These catalyze the electro-oxidation of hydroquinone (HQ) and catechol (CT). The peak-to-peak separation is around 109 mV, while a bare GCE cannot resolve the peaks (located at 165 and 274 mV vs. Ag/AgCl). Sensitivity is also enhanced to ∼1.20 and 1.19 µA·cm-2·µM-1, respectively. The sensor has a linear response that covers the 20-250 µM concentration range for both HQ and CT, with 0.75 and 0.76 µM detection limits, respectively, at simultaneous detection. Commonly present species do not interfere. Graphical abstract A novel conducting poly(2,4-dinitrophenylhydrazine)-modified anodized glassy carbon electrode (pDNPH/AGCE) was developed by electrochemical method. The electro-catalytic activity of pDNPH/AGCE sensor was investigated for the selective and simultaneous electrochemical detection of hydroquinone (HQ) and catechol (CT), which revealed high sensitivities and low detection limits with excellent stability.

Studies of Grafted and Sulfonated Spiro Poly(isatin-ethersulfone) Membranes by Super Acid-Catalyzed Reaction.

Spiro poly(isatin-ethersulfone) polymers were prepared from isatin and bis-2,6-dimethylphenoxyphenylsulfone by super acid catalyzed polyhydroxyalkylation reactions. We designed and synthesized bis-2,6-dimethylphenoxyphenylsulfone, which is structured at the meta position steric hindrance by two methyl groups, because this structure minimized crosslinking reaction during super acid catalyzed polymerization. In addition, sulfonic acid groups were structured in both side chains and main chains to form better polymer chain morphology and improve proton conductivity. The sulfonation reactions were performed in two steps which are: in 3-bromo-1-propanesulfonic acid potassium salt and in con. sulfuric acid. The membrane morphology was studied by tapping mode atomic force microscope (AFM). The phase difference between the hydrophobic polymer main chain and hydrophilic sulfonated units of the polymer was shown to be the reasonable result of the well phase separated structure. The correlations of proton conductivity, ion exchange capacity (IEC) and single cell performance were clearly described with the membrane morphology.