Propylene Carbonate Research Articles

Understanding the Role of Imide-Based Salts and Borate-Based Additives for Safe and High-Performance Glyoxal-Based Electrolytes in Ni-Rich NMC811 Cathodes for Li-Ion Batteries.

Herein, the design of novel and safe electrolyte formulations for high-voltage Ni-rich cathodes is reported. The solvent mixture comprising 1,1,2,2-tetraethoxyethane and propylene carbonate not only displays good transport properties, but also greatly enhances the overall safety of the cell thanks to its low flammability. The influence of the conducting salts, that is, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium bis(fluorosulfonyl)imide (LiFSI), and of the additives lithium bis(oxalato)borate (LiBOB) and lithium difluoro(oxalato)borate (LiDFOB) is examined. Molecular dynamics simulations are carried out to gain insights into the local structure of the different electrolytes and the lithium-ion coordination. Furthermore, special emphasis is placed on the film-forming abilities of the salts to suppress the anodic dissolution of the aluminum current collector and to create a stable cathode electrolyte interphase (CEI). In this regard, the borate-based additives significantly alleviate the intrinsic challenges associated with the use of LiTFSI and LiFSI salts. It is worth remarking that a superior cathode performance is achieved by using the LiFSI/LiDFOB electrolyte, displaying a high specific capacity of 164mAhg-1 at 6C and ca. 95% capacity retention after 100 cycles at 1C. This is attributed to the rich chemistry of the generated CEI layer, as confirmed by ex situ X-ray photoelectron spectroscopy.

ZnGA/DMC catalysts for the synthesis of high molecular weight poly(propylene carbonate): The crucial role of water treatment

Zinc glutarate (ZnGA) is a prominent catalyst for the production of CO2-based poly(propylene carbonate). The original catalysts, ZnO-GA (Cat 1) and ZnAc2-GA (Cat 3), were prepared using ZnO and ZnAc2 as Zn sources, respectively. ZnO-GA-H2O (Cat 2) and ZnAc2-GA-H2O (Cat 4) were prepared by water treatment of Cat 1 and Cat 3, respectively. After water treatment, both Cat 2 and Cat 4 showed enhanced performance for copolymerization of CO2 and propylene oxide. The characterizations demonstrated that H2O is a critical component that not only improves the crystallinity and external surface area of ZnGA, but also increases the number of surface Zn-OH groups. By adding a portion of cyanide, further modification on Cat 4 resulted in a group of ZnAc2-GA-H2O/DMC catalysts (m-Cat 4). The polymerization reached a high yield of 1729 g poly/g Cat and a selectivity of 98.7 % at molar ratio of DMC/ZnGA = 1: 10 (t = 24 h; T = 70 °C; P = 4 MPa). The modified ZnGA/DMC catalyst exhibited remarkable yield and selectivity for the copolymerization of CO2 and propylene oxide to produce high molecular weight alternating copolymers (2.3 × 105 g/mol).

Fabricating Wide‐Temperature‐Range Quasi‐Solid Sodium Batteries with Fast Ion Transport via Tin Additives

AbstractQuasi‐solid sodium batteries, employing quasi‐solid polymer electrolytes (QSPEs) renowned for their high energy density and cost‐effective fabrication, are promising candidates for next‐generation energy storage systems. However, their practical application has encountered impediments such as insufficient ion transport and uneven sodium plating/stripping attributed to suboptimal interfacial compatibility. In this work, an innovative QSPE is developed by incorporating functional additives, specifically fluoroethylene carbonate (FEC) and tin trifluoromethanesulfonate (Sn(OTf)2), into the poly(vinylidenefluoride‐co‐hexafluoropropylene) (PVDF‐HFP)/propylene carbonate (PC) polymer electrolyte. Sn(OTf)2 catalyzes a ring‐opening reaction in PC, thereby reducing transmission barriers and augmenting the transport of sodium ions. Consequently, the resulting HFP‐PC‐FEC‐Sn QSPE demonstrates remarkable ionic conductivity (0.42 mS cm─1) and ion transference number (0.58). Furthermore, it forms a dense and smooth interphase enriched with NaF and metallic Sn, significantly enhancing the long‐term cycling stability of Na symmetric cells, which endure over 3000 h at 0.2 mA cm─2, and effectively suppressing the formation of sodium dendrites. This outstanding electrochemical performance extends to Na3V2(PO4)3/Na full coin and pouch cells across a wide temperature range. This work introduces an innovative approach for designing high‐performance QSPEs suitable for wide‐temperature quasi‐solid sodium batteries.

A Microporous Gel Polymer Electrolyte with High Mg2+ Ionic Conductivity at Room Temperature

AbstractRechargeable magnesium batteries have attracted much attention due to the high theoretical volumetric capacity, abundance, and safety. However, solid‐state Mg batteries have been rarely studied because of limited choices of solid‐state electrolyte materials. In this research, poly(vinylidene fluoride)/poly(propylene carbonate) (PVDF/PPC) as matrix were prepared using a simple solution casting method. Ethylene carbonate (EC), diethyl carbonate (DEC), and magnesium(II) bis(trifluoromethanesulfonyl) imide [Mg(TFSI)2] were selected to prepare liquid electrolyte. A classification of novel gel polymer electrolytes (GPEs), PVDF/PPC/Mg(TFSI)2, was synthesized and investigated. The electrochemical measurements show that PVDF/PPC/Mg(TFSI)2 polymer electrolytes exhibit a high ionic conductivity, close to 10−2 S cm−1, at room temperature. The electrochemical stability window of PVDF/PPC‐based GPE was up to 3 V (versus Mg2+/Mg). Materials characterization shows that these GPEs have a porous structure, providing a pathway for magnesium ion transport. Thermal analysis and crystal structure results indicate that PVDF crystallinity was affected by the addition of PPC. Additionally, the ion transport mechanism in the gel polymer electrolyte has been discussed.

Nonlinear dielectric response in glass formers: Restoring forces and avoided spin-glass criticality.

Experimental measurements of nonlinear dielectric response in glass formers like supercooled glycerol or propylene carbonate have been interpreted as providing evidence for a growing thermodynamic length scale when lowering temperature. A heuristic picture based on coherently flipping "superdipoles" with disordered internal structure has been argued to capture the essence of the experimentally reported behavior, pointing to the key role of effectively disordered interactions in structural glasses. We test these ideas by devising an explicit one-dimensional model of interacting spins incorporating both the spin-glass spirit of the superdipole argument and the necessary long-time decorrelation of structural disorder, encoded here in a slow dynamics of the coupling constants. The frequency-dependent third-order response of the model qualitatively reproduces the typical humped shape reported in experiments. The temperature dependence of the maximum value is also qualitatively reproduced. In contrast, the humped shape of the third-order response is not reproduced by a simple kinetically constrained spin model with noninteracting spins. To rationalize these results, we propose a two-length-scale scenario by distinguishing between the characteristic length of dynamical heterogeneities and a rigidity length that accounts for the local tendency of spins to flip coherently as a block, in the presence of interactions. We show that both length scales are identical in the kinetically constrained spin model, while they have significantly different dynamics in the model of interacting spins.

LaFeO3 nanoparticle immobilized on DFNS-graphene oxide for the production of polymer and biopolyurethanes from carbon dioxide

Dendritic fibrous nano silica (DFNS) was functionalized through the utilization of graphene oxide (GO) as a long-lasting anchoring agent. Consequently, the LaFeO3 nanoparticles were evenly spread out without clumping over the DFNS/GO. The supramolecular polymerized GO served the dual purpose of preventing the restacking of graphene sheets and functioned as a supplier of nitrogen to create active sites for the bonding of LaFeO3 nanoparticles. The nitrogen content above the extent of the GO films was modified by LaCl3·7 H2O and Fe(NO3)3·9H2O ions to synthesize LaFeO3 nanoparticles. The catalytic properties of DFNS/GO-LaFeO3 was observed in the reaction between CO2 and oxetane and epoxide, leading to the production of the corresponding polycarbonates. The results indicated that DFNS/GO-LaFeO3 significantly enhanced the efficiency of synthesizing poly(propylene carbonate) and poly(trimethylene carbonate) from carbon dioxide. This approach offers substantial benefits, including high economic efficiency. The union reaction of CO2 and highly substituted epoxides sourced from sustainable sources such as discarded vegetable oils and fatty acids resulted in the production of novel cyclic carbonates of bio-origin. This reaction occurred under gentle and solvent-free conditions using DFNS/GO-LaFeO3 as a catalyst. The DFNS/GO-LaFeO3 exhibited a high capacity for CO2 uptake with exceptionally rapid kinetics. The nanoplate morphology of DFNS/GO-LaFeO3 facilitated the formation of a satisfactory outer layer for carbon dioxide uptake at each metal site. Consequently, the nanoplate morphology of DFNS/GO-LaFeO3 ensured systematic carbon dioxide emission, guaranteeing a complete reaction with the entire sheet and enabling rapid CO2 adsorption kinetics.

Ethylene-vinyl acetate/poly (propylene carbonate) nanocomposites: effects of graphene oxide on microstructure, shape memory, and mechanical characteristics

Ethylene-vinyl acetate/poly (propylene carbonate) nanocomposites: effects of graphene oxide on microstructure, shape memory, and mechanical characteristics

Carbon Dioxide-Derived Poly(Propylene Carbonate) Bottlebrush Polymers: Synthesis, Viscoelastic Properties, and Degradation

Carbon Dioxide-Derived Poly(Propylene Carbonate) Bottlebrush Polymers: Synthesis, Viscoelastic Properties, and Degradation

Fast-Curing 3-Layer Particleboards with Lignosulfonate and pMDI Adhesives

Currently, the industrial success of bio-based adhesives remains limited, despite the growing interest in these compounds. One example is the use of lignosulfonates (LS), a byproduct from the pulp and paper industry, which requires long pressing times to ensure proper performance for wood-based panel production. This study successfully manufactured particleboards using a low press factor of 7.5 s/mm, commonly used for conventional urea-formaldehyde resins on a lab scale. To the best of our knowledge, lignin-based particleboards have never been reported using such low press factors. Thus, 3-layer boards were manufactured in which the core layer was bonded with polymeric isocyanate (pMDI), and the surface layers were bonded with LS. Propylene carbonate (PC) was used as a solvent for pMDI to improve adhesive distribution. The optimum amounts of adhesive were determined using response surface methodology: 1.3% pMDI with 2.2% PC in the core layer and 15% LS in the surface layers. These boards obeyed the requirements of standard EN 312 for general-purpose boards for use in dry conditions (type P1). Their formaldehyde content, determined through the perforator method, was equal to that of the wood mix at the maximum value set by IKEA for class E0.5.

Effect of Layered Double Hydroxide and Its Localization on the Structure and Properties of PBAT/PPC Composites

AbstractThe blends of poly(butylene adipate‐co‐terephthalate) (PBAT), poly(propylene carbonate) (PPC), chain extender (ADR) and layered double hydroxides (LDH) are prepared by different extrusion methods. Effects of LDH and its distribution on rheology, phase morphology, mechanical properties, water vapor barrier properties and food preservation properties are investigated. Results show that when PBAT, PPC, and LDH are mixed directly, LDH is preferentially distributed in the PBAT phase. When LDH are mixed with PPC firstly and then further with PBAT, LDH mostly migrates to the interface of PBAT and PPC. The epoxy groups of ADR react with the terminal groups of the polymers to improve the interfacial compatibility. Adding LDH, the mechanical properties and barrier properties of the materials are improved and by premixing of PPC and LDH, properties of composites are further improved. Compared with PBAT/PPC blends, the tensile strength and elongation at break of PBAT/PPC(LDH‐0.5)/ADR increased by 25.2% and 15.3%, respectively. The banana packaged in PBAT/PPC/LDH films maintains good freshness. It illustrates that PBAT/PPC(LDH)/ADR composites have a good application prospect in the field of barrier and food packaging based on their excellent mechanical, barrier, and preservation properties.

Synergetic Dual-Additive Electrolyte Enables Highly Stable Performance in Sodium Metal Batteries.

Sodium (Na)-metal batteries (SMBs) are considered one of the most promising candidates for the large-scale energy storage market owing to their high theoretical capacity (1,166 mAh g-1) and the abundance of Na raw material. However, the limited stability of electrolytes still hindered the application of SMBs. Herein, sulfolane (Sul) and vinylene carbonate (VC) are identified as effective dual additives that can largely stabilize propylene carbonate (PC)-based electrolytes, prevent dendrite growth, and extend the cycle life of SMBs. The cycling stability of the Na/NaNi0.68Mn0.22Co0.1O2 (NaNMC) cell with this dual-additive electrolyte is remarkably enhanced, with a capacity retention of 94% and a Coulombic efficiency (CE) of 99.9% over 600 cycles at a 5 C (750mA g-1) rate. The superior cycling performance of the cells can be attributed to the homogenous, dense, and thin hybrid solid electrolyte interphase consisting of F- and S-containing species on the surface of both the Na metal anode and the NaNMC cathode by adding dual additives. Such unique interphases can effectively facilitate Na-ion transport kinetics and avoid electrolyte depletion during repeated cycling at a very high rate of 5 C. This electrolyte design is believed to result in further improvements in the performance of SMBs.

An innovative approach to develop plant-derived and CO2-based active biocomposite films towards antioxidant activity

In this study, novel biocomposites composed of CO2-derived poly(propylene) carbonate and plant-based cellulose were developed employing solvent casting technique. An innovative and rapid strategy was employed, whereby pre-dissolving cellulose improves dramatically the compatibility of poly(propylene) carbonate with cellulose whilst pristine cellulose powder displays inhomogeneous distributions of cellulose within the biocomposite. Resulting biocomposites produce flat homogeneous surfaces with low cellulose content, whilst rougher surfaces and thicker cross sections were observed in films with higher cellulose content. Developed biocomposites outperformed biocomposites produced from pristine cellulose powder in terms of homogeneity, thermal stability, antioxidant activity and biocompatibility. Higher cellulose content samples show the formation of a new hydrogen bonding network between PPC and cellulose polymer chains and this contributes to improved thermal stability. TGA results reveal improved thermal stability for high cellulose content films and show enhanced water vapor permeability. A cell viability study shows that the developed materials are biocompatible. Curcumin, a natural antioxidant, was incorporated into optimized biocomposites to produce active biocomposites with antioxidant features to accelerate wound healing. Curcumin is shown to display a sustained release profile over a time period of 3 days, and this is ideal for would healing. The curcumin-functionalized biocomposites also contributed to enhanced thermal stability and water vapor permeability. Thus, these biocomposite films show promise as active biocomposites which can be used for biomedical applications such as wound healing.

A difunctional electrolyte boosting the electrochemical performance of the primary Li/CFx batteries

Lithium/carbon fluorides (Li/CFx) batteries have received widespread attention because of the advantages of high energy density, low environmental pollution, and low self-discharge. However, less attention has been paid to electrolytes which also significantly affect the electrochemical performance of Li/CFx batteries. Herein, we develop a novel electrolyte for Li/CFx batteries, a mixture of lithium bis-(trifluoromethanesulfonyl)imide (LiTFSI) and lithium difluoro(oxalate) borate (LiODFB) with different ratios dissolving in propylene carbonate (PC)/methyl butyrate (MB). Interestingly, the LiODFB not only boosts the specific capacity exceeding the theoretical value (865 mAh−1) by introducing extra capacity via its ring opening reaction with Li+ during the discharge process, but also enhances the discharge voltage and rate capability at varying temperature. As expected, the Li/CFx batteries with electrolyte of 1 M LiODFB in PC/MB delivers an ultrahigh specific capacity of 1169.84 mAh g−1 and energy density of 2646.93 Wh kg−1 at 30 °C and 10 mA g−1, and 966.9 mAh g−1 and 2232.8 Wh kg−1 at 70 ℃ and 500 mA g−1, respectively. These findings provide new ideas on designing Li/CFx batteries with high capacity and high energy density.

Sustainable and Safe N-alkylation of N-heterocycles by Propylene Carbonate under Neat Reaction Conditions.

A new, eco-friendly process utilising the green solvent propylene carbonate (PC) has been developed to perform N-alkylation of N-, O- and/or S-containing heterocyclic compounds. PC in these reactions served as both the reagent and solvent. Importantly, no genotoxic alkyl halides were required. No auxiliary was necessary when using anhydrous PC. Product formation includes nucleophilic substitution with the concomitant loss of water and carbon dioxide. Substrates prepared, including the newly invented PROTAC drugs, are widely used.

Exploring relaxation behaviors in Hydrogen-Bond networks within binary mixtures of propylene carbonate and primary alcohols through broadband dielectric spectroscopy and molecular dynamic simulation

This work investigates the dielectric properties and the relaxation behaviors of propylene carbonate (PC) and its binary mixtures with methanol and ethanol. A coaxial-circular cutoff waveguide junction was employed to characterize broadband dielectric spectra ranging from 0.1 GHz to 18 GHz, and a two-group Debye model was used to extract relaxation parameters. Excess thermodynamic parameters, Kirkwood orientational correlation factors, and Bruggeman factors for PC-alcohol mixtures were also analyzed and presented. These data provide insights into microscopic dynamic processes as the PC concentration in the mixtures gradually increases. These processes include the continuous disassociation of the alcohols’ hydrogen-bond (H-bond) networks, the formation of new PC-alcohol H-bond networks, the parallel alignment of heterogeneous dipoles, and a significant enhancement of the dielectric effect. Furthermore, a series of molecular dynamics (MD) simulations using the TraPPE-UA forcefield were conducted, and the obtained thermodynamic and electromagnetic parameters demonstrated good agreement with experimental results. Based on radial distribution functions, dipole–dipole spatial orientational correlations, and H-bond life times extracted from the MD simulations, we observed the gradual formation of PC-cage and alcohol-cluster microstructures in PC-rich mixtures. The data and physical insights provided in this work are expected to have practical implications in high-energy battery applications and the pharmaceutical industry.

Hydrolytic degradation behaviors of polylactides/poly(propylene carbonate blends: Monolayers and bulk films

The study investigates the hydrolytic degradation behaviors of blends comprising polylactides (PLA) and poly(propylene carbonate) (PPC) in the form of monolayers and bulk films. PLA is a biodegradable polymer widely used in various applications, while PPC offers unique properties, making it a promising candidate for blend formulations. The research explores the degradation kinetics and mechanical properties under controlled hydrolysis conditions. The finding focuses on the compatibility of PLA and PPC, their degradation mechanisms, and the impact of blend composition on degradation rates. Understanding the hydrolytic behavior of these blends is crucial for designing eco-friendly materials with tailored degradation profiles for diverse applications.

Engineering the Activity and Stability of the Zn-MOF Catalyst via the Interaction of Doped Zr with Zn.

Metallic atoms within metal-organic framework (MOF) materials exhibit a distinctive and adaptable coordination structure. The three-dimensional (3D) pore configuration of MOFs enables the complete exposure of metal active sites, rendering them prevalent in various catalytic reactions. In this study, zinc (Zn) atoms within Zn-based MOF materials, characterized by an abundance of valence electrons, are utilized for the transesterification of dimethyl carbonate (DMC). Additionally, the introduction of zirconium (Zr) effectively addresses the susceptibility of the MOFs' crystal structure to dissolution in organic solvents. The formulated catalyst, Zn-10%Zr-MOF(300), demonstrates remarkable catalytic performance with 91.5% DMC selectivity, 61.9% propylene carbonate (PC) conversion, and 56.6% DMC yield. Impressively, the catalyst maintains its high performance over five cycles. Results indicate that Zr interacts with Zn, forming new coordination bonds and enhancing the catalyst crystal structure stability. Moreover, electron transfer intensifies the alkalinity of the active Zn atoms, enhancing the overall catalyst performance. This research informs the development of transesterification heterogeneous catalysts and broadens the application scope of MOF catalysts.

Unveiling a Novel Decomposition Pathway in Propylene Carbonate-Based Supercapacitors: Insights from a Jelly Roll Configuration Study.

This research elucidates novel insights into the electrochemical properties and degradation phenomena of propylene carbonate (PC)-based supercapacitors at a large-scale 18650 cylindrical jelly-roll cell level. Central to our findings is the identification of 2-ethyl-4-methyl-1,3-dioxolane (EMD) as a hitherto undocumented decomposition by-product, highlighting the nuanced complexity of PC electrolyte stability. We further demonstrate that elevated operational voltages precipitate accelerated electrolyte degradation, underscoring the criticality of defining the operational voltage window for maximizing device longevity. Employing advanced analytical techniques, including gas chromatography-mass spectrometry (GC-MS), this study meticulously analyzes electrolyte decomposition mechanisms. The outcomes offer pivotal insights into the operational constraints and chemical resilience of PC-based supercapacitors, contributing significantly to the optimization of supercapacitor design and application. By delineating a specific decomposition pathway, this investigation enriches the understanding of electrochemical dynamics in supercapacitor systems, providing a foundation for future research and technological advancement in energy storage devices.

Unveiling the Impact of Tailoring Ionic Conductor Characteristics on the Performance of Wearable Triboelectric Nanogenerators.

This work reveals the correlation between the performance of triboelectric nanogenerators (TENGs) and the characteristics of deformable solid-state ionic conductors (referred to as ionogels). For this purpose, we modify ionogel characteristics by incorporating additional plasticizers (propylene carbonate) and solid salts (lithium bis(trifluoromethylsulfonyl)imide) into the ionogels. We conclude that the high capacitance of the ionogel is crucial for achieving a high-performance TENG platform. The optimized ionogel-based TENG (i-TENG) exhibits a power density of ∼372.4 mW·m-2 (based on 95 V and 36 mA·m-2 outputs) with outstanding long-term stability over 2 weeks. Additionally, successful demonstrations of wearable nanogenerators are performed by leveraging the high stretchability (up to ∼1000%) and optical transparency (∼90%) of the ionogels. Overall, the results provide insight into the design of deformable ionic conductors for high-performance, reliable, and wearable TENGs.

Preparing a microemulsion-loaded hydrogel for cleaning wall paintings and coins

Removing unwanted materials, such as organic coatings and soil, from the cultural relic surface is a complex and significant task in the field of cultural heritage conservation. Microemulsion-loaded gel can effectively and safely remove those organic coatings and soil. Here, we employed a simple solvent exchange strategy to prepare a microemulsion-loaded polyvinyl alcohol/polyethyleneimine (PVA/PEI) hydrogel. First, PVA and PEI were dissolved into DMSO to form a gel. Then, the gel was immersed into a microemulsion composed of water, ethyl acetate, propylene carbonate, sodium dodecyl sulfate, and 1-pentanol to exchange DMSO. Microemulsion-loaded PVA/PEI hydrogel can be synthesized by completely substituting DMSO. To investigate the microstructure, rheological properties, and mechanical properties of the gel, scanning electron microscopy, a rheometer, and a universal testing machine were used, respectively. Fourier transform infrared (FT-IR) analysis was conducted to explore the synthesis mechanism and confirm the successful loading of microemulsion within the microemulsion-loaded PVA/PEI hydrogel. Furthermore, FT-IR, a depth-of-field microscope, and a glossmeter were utilized to evaluate the cleaning efficiency of the microemulsion-loaded PVA/PEI hydrogel for removing animal glue and soil from the surfaces of cultural relics. Moreover, an X-ray fluorescence spectrometer was used to analyze the element component of the ancient coin. The application results showed that the microemulsion-loaded PVA/PEI hydrogel can effectively remove animal glue from an ancient wall painting surface. Moreover, it is capable of removing soil from an ancient coin surface as well, which helped to confirm the age of the coin. This offers a novel method to prepare microemulsion-loaded hydrogel and demonstrates great potential in the cleaning for cultural heritage.