Sulfide-based all-solid-state battery (ASSB) with a lithium metal anode (LMA) is a promising candidate to surpass conventional Li-ion batteries owing to their inherent safety against fire hazards and potential to achieve a higher energy density. However, the narrow electrochemical stability window and chemical reactivity of the sulfide solid electrolyte towards the LMA results in interfacial degradation and poor electrochemical performance. In this direction, we introduce an organic additive approach, that is the mixing of prelithiated trithiocyanuric acid, Li3TCA, with Li6PS5Cl, to establish a stable interface while preserving high ionic conductivity. Including 2.5 wt% Li3TCA alleviates the decomposition of the electrolyte on the lithium metal interface, decreasing the Li2S content in the solid-electrolyte interface (SEI) thus forming a more stable interface. In Li|Li symmetric cells this enables a rise in the critical current density from 1.0 to 1.9 mA cm-2 and stable cycling for over 750 hours at a high current density of 1.0 mA cm-2. This approach also enables Li|NbO-NCM811 full cell to operate more than 500 cycles at 0.3C.
Cellulose nanocrystals (CNCs) are bio-based, rod-like, high-aspect-ratio nanoparticles with high stiffness and strength and are widely used as a reinforcing nanofiller in polymer nanocomposites. However, due to hydrogen-bond formation between the large number of hydroxyl groups on their surface, CNCs are prone to aggregate, especially in nonpolar polymer matrices. One possibility to overcome this problem is to graft polymers from the CNCs' surfaces and to process the resulting "hairy nanoparticles" (HNPs) into one-component nanocomposites (OCNs) in which the polymer matrix and CNC filler are covalently connected. Here, we report OCNs based on HNPs that were synthesized by grafting gradient diblock copolymers onto CNCs via surface-initiated atom transfer radical polymerization. The inner block (toward the CNCs) is composed of poly(methyl acrylate) (PMA), and the outer block comprises a gradient copolymer rich in poly(methyl methacrylate) (PMMA). The OCNs based on such HNPs microphase separate into a rubbery poly(methyl acrylate) phase that dissipates mechanical energy and imparts toughness, a glassy PMMA phase that provides strength and stiffness, and well-dispersed CNCs that further reinforce the materials. This design afforded OCNs that display a considerably higher stiffness and strength than reference diblock copolymers without the CNCs. At the same time, the extensibility remains high and the toughness is increased up to 5-fold relative to the reference materials.
Acrylates , Nanocomposites , Nanoparticles , Cellulose/chemistry , Polymethyl Methacrylate , Polymers/chemistry , Nanoparticles/chemistry , Nanocomposites/chemistry
We report the synthesis of two-dimensional and three-dimensional porous polyphenylenes (2D/3D-pPPs) via the Diels-Alder cycloaddition polymerization reaction. The resulting 2D and 3D-pPPs showed surface areas up to 1553 m2 g-1, pore volumes of 1.45 cm3 g-1 and very high H2 uptake capacities of 7.4 and 7.1 wt% at 77 K, respectively, along with a competitive high-pressure CO2 and CH4 uptake performance.
Palladium (Pd) recycling from waste materials is an important approach in order to meet the growing demand for Pd originating from its broad range of applications including automotive industry, electronics and catalysis. In this article, we discuss the design principles of solid-sorbents for efficient recovery of Pd from waste sources with a particular emphasis on porous organic polymers (POPs), which emerged as promising porous materials for Pd recovery due to their tunable chemical functionality, stability and porosity. We discuss the critical role of binding sites and porosity in the Pd uptake capacity, adsorption kinetics and selectivity. We also highlight the use of captured Pd within the polymer networks as heterogeneous catalysts for cross-coupling reactions.
Phthalocyanines (PCs) are intriguing building blocks owing to their stability, physicochemical and catalytic properties. Although PC-based polymers have been reported before, many suffer from relatively low stability, crystallinity, and low surface areas. Utilizing a mixed-metal salt ionothermal approach, we report the synthesis of a series of metallophthalocyanine-based covalent organic frameworks (COFs) starting from 1,2,4,5-tetracyanobenzene and 2,3,6,7-tetracyanoanthracene to form the corresponding COFs named M-pPPCs and M-anPPCs, respectively. The obtained COFs followed the Irving-Williams series in their metal contents, surface areas, and pore volume and featured excellent CO2 uptake capacities up to 7.6â mmol g-1 at 273â K, 1.1â bar. We also investigated the growth of the Co-pPPC and Co-anPPC on a highly conductive carbon nanofiber and demonstrated their high catalytic activity in the electrochemical CO2 reduction, which showed Faradaic efficiencies towards CO up to 74 % at -0.64â V vs. RHE.
We addressed the poor interfacial stability of the Li metal anode in Li-S batteries through molecular regulation of electrolytes using arylthiol additives with various numbers of anchoring sites. The dual functional tetrathiol additive markedly enhanced the Li anode interfacial stability, controlled the sulfur redox kinetics and suppressed side reactions towards polysulfides, thus leading to an improved capacity retention of 70% after 500 cycles at 1 C.
Electrolytes , Lithium , Electric Power Supplies , Electrodes , Sulfur
Porous organic polymers (POPs) have gained tremendous attention owing to their chemical tunability, stability and high surface areas. Whereas there are several examples of fully conjugated two-dimensional (2D) POPs, three-dimensional (3D) ones are rather challenging to realize in the absence of structural templates. Herein, we report the base-catalyzed direct synthesis of a fully conjugated 3D POPs, named benzyne-derived polymers (BDPs), containing biphenylene and tetraphenylene moieties starting from a simple bisbenzyne precursor, which undergoes [2+2] and [2+2+2+2] cycloaddition reactions to form BDPs primarily composed of biphenylene and tetraphenylene moieties. The resulting polymers exhibited ultramicroporous structures with surface areas up to 544â m2 g-1 and very high CO2 /N2 selectivities.
Conventional synthetic strategies do not allow one to impart structural anisotropy into porous carbons, thus leading to limited control over their textural properties. While structural anisotropy alters the mechanical properties of materials, it also introduces an additional degree of directionality to increase the pore connectivity and thus the flux in the designed direction. Accordingly, in this work the structure of porous carbons prepared from resorcinol-formaldehyde gels has been rendered anisotropic by integrating superparamagnetic colloids to the sol-gel precursor solution and by applying a uniform magnetic field during the sol-gel transition, which enables the self-assembly of magnetic colloids into chainlike structures to template the growth of the gel phase. Notably, the anisotropic pore structure is maintained upon pyrolysis of the gel, leading to hierarchically porous carbon monoliths with tunable structure and porosities. With an advantage granted to anisotropic materials, these porous carbons showed higher porosity, a higher CO2 uptake capacity of 3.45 mmol g-1 at 273 K at 1.1 bar, and faster adsorption kinetics compared to the ones synthesized in the absence of magnetic field. Moreover, these materials were also used as magnetic sorbents with fast adsorption kinetics for efficient oil-spill cleanup and retrieved easily by using an external magnetic field.
Fluorination of ether solvents is an effective strategy to improve the electrochemical stability of non-aqueous electrolyte solutions in lithium metal batteries. However, excessive fluorination detrimentally impacts the ionic conductivity of the electrolyte, thus limiting the battery performance. Here, to maximize the electrolyte ionic conductivity and electrochemical stability, we introduce the targeted trifluoromethylation of 1,2-dimethoxyethane to produce 1,1,1-trifluoro-2,3-dimethoxypropane (TFDMP). TFDMP is used as a solvent to prepare a 2 M non-aqueous electrolyte solution comprising bis(fluorosulfonyl)imide salt. This electrolyte solution shows an ionic conductivity of 7.4 mS cm-1 at 25 °C, an oxidation stability up to 4.8 V and an efficient suppression of Al corrosion. When tested in a coin cell configuration at 25 °C using a 20 µm Li metal negative electrode, a high mass loading LiNi0.8Co0.1Mn0.1O2-based positive electrode (20 mg cm-2) with a negative/positive (N/P) capacity ratio of 1, discharge capacity retentions (calculated excluding the initial formation cycles) of 81% after 200 cycles at 0.1 A g-1 and 88% after 142 cycles at 0.2 A g-1 are achieved.
Switchable gas separation membranes are intriguing systems for regulating the transport properties of gases. However, existing stimuli-responsive gas separation membranes suffer from either very slow response times or require high energy input for switching to occur. Accordingly, herein, we introduced light-switchable polymeric carbon nitride (pCN) gas separation membranes with fast response times prepared from melamine precursor through in-situ formation and deposition of pCN onto a porous support using chemical vapor deposition. Our systematic analysis revealed that the gas transport behavior upon light irradiation is fully governed by the polarizability of the permeating gas and its interaction with the charged pCN surface, and can be easily tuned either by controlling the power of the light and/or the duration of irradiation. We also demonstrated that gases with higher polarizabilities such as CO2 can be separated from gases with lower polarizability like H2 and He effectively with more than 22% increase in the gas/CO2 selectivity upon light irradiation. The membranes also exhibited fast response times (<1 s) and can be turned "on" and "off" using a single light source at 550 nm.
Porous organic polymers (POPs) have long been considered as prime candidates for carbon dioxide (CO2) capture, separation, and conversion. Especially their permanent porosity, structural tunability, stability and relatively low cost are key factors in such considerations. Whereas heteratom-rich microporous networks as well as their amine impregnation/functionalization have been actively exploited to boost the CO2 affinity of POPs, recently, the focus has shifted to engineering the pore environment, resulting in a new generation of highly microporous POPs rich in heteroatoms and featuring abundant catalytic sites for the capture and conversion of CO2 into value-added products. In this review, we aim to provide key insights into structure-property relationships governing the separation, capture and conversion of CO2 using POPs and highlight recent advances in the field.
Carbon Dioxide , Polymers , Porosity , Carbon Dioxide/chemistry , Polymers/chemistry , Amines/chemistry
There exists an urgent demand for the advancement of technologies that reduce and capture carbon dioxide (CO2) emissions to mitigate anthropogenic contributions to climate change. This paper compares the maximum power densities achieved from the combination of reverse electrodialysis (RED) with carbon capture (CC) using various CC solvents. Carbon capture reverse electrodialysis (CCRED) harvests energy from the salinity gradients generated from the reaction of CO2 with specific solvents, generally amines. To eliminate the requirement of freshwater as an external resource, we took advantage of a semiclosed system that would allow the inputs to be industrial emissions and heat and the outputs to be electrical power, clean emissions, and captured CO2. We assessed the power density that can be attained using CCRED with five commonly studied CC solvents: monoethanolamine (MEA), diethanolamine (DEA), N-methyldiethanolamine (MDEA), 2-amino-2-methyl-2-propanol (AMP), and ammonia. We achieved the highest power density, 0.94 W m-2 cell-1, using ammonia. This work provides a foundation for future iterations of CCRED that may help to incentivize adoption of CC technology.
BACKGROUND: The COVID-19 pandemic started to affect Turkey in March 2020. In this study, we retrospectively investigated spontaneous rectus sheath hematoma (S-RSH) in patients with COVID-19 presenting with acute abdominal pain during the ongoing pandemic. METHODS: The demographic characteristics, laboratory findings, length of hospital stay, and treatment processes of COVID-19 cases with S-RSH detected between March and December 2020 were recorded. The rectus sheath hematoma diagnosis of the patients was made using abdominal computed tomography, and the patients were followed up. Low-molecular-weight heparin treatment, which was initiated upon admission, was continued during the follow-up. RESULTS: S-RSH was detected in 13 out of 220 patients with COVID-19 who were referred to general surgery for consultation due to acute abdominal pain. The mean age of these patients was 78±13 years, and the female-to-male ratio was 1.6. Mechanical ven-tilation support was applied to three patients, all of whom were followed up in the intensive care unit. Two patients died for reasons independent of rectus sheath hematoma during their treatment. Among the laboratory findings, the activated partial thromboplastin time (aPTT) values did not deviate from the normal range. While there was no correlation between the international normalized ratio (INR) and aPTT (p>0.01), a significant correlation was found between INR and interleukin-6 (IL-6) (p<0.002). None of the patients required surgical or endovascular interventional radiology procedures. CONCLUSION: In the literature, the incidence of S-RSH in patients presenting with acute abdominal pain is 1.8%. However, in our series, this rate was approximately 3 times higher. Our patients' normal INR and aPTT values suggest that coagulopathy was mostly secondary to endothelial damage. In addition, the significantly higher IL-6 values (p<0.002) indicate the development of vasculitis along with the acute inflammatory process. S-RSH can be more commonly explained the high severity of vasculitis and endothelial damage due to viral infection.
Abdomen, Acute , COVID-19 , Muscular Diseases , Vasculitis , Abdomen, Acute/epidemiology , Abdominal Pain/etiology , Aged , Aged, 80 and over , Female , Hematoma/diagnostic imaging , Hematoma/epidemiology , Hematoma/etiology , Humans , Incidence , Interleukin-6 , Male , Muscular Diseases/diagnosis , Muscular Diseases/epidemiology , Muscular Diseases/etiology , Pandemics , Rectus Abdominis/diagnostic imaging , Retrospective Studies , Vasculitis/complications , Vasculitis/epidemiology
The development of new solvents is imperative in lithium metal batteries due to the incompatibility of conventional carbonate and narrow electrochemical windows of ether-based electrolytes. Whereas the fluorinated ethers showed improved electrochemical stabilities, they can hardly solvate lithium ions. Thus, the challenge in electrolyte chemistry is to combine the high voltage stability of fluorinated ethers with high lithium ion solvation ability of ethers in a single molecule. Herein, we report a new solvent, 2,2-dimethoxy-4-(trifluoromethyl)-1,3-dioxolane (DTDL), combining a cyclic fluorinated ether with a linear ether segment to simultaneously achieve high voltage stability and tune lithium ion solvation ability and structure. High oxidation stability up to 5.5 V, large lithium ion transference number of 0.75 and stable Coulombic efficiency of 99.2% after 500 cycles proved the potential of DTDL in high-voltage lithium metal batteries. Furthermore, 20 µm thick lithium paired LiNi0.8Co0.1Mn0.1O2 full cell incorporating 2 M LiFSI-DTDL electrolyte retained 84% of the original capacity after 200 cycles at 0.5 C.
Ether-based electrolytes offer promising features such as high lithium-ion solvation power and stable interface, yet their limited oxidation stability impedes application in high-voltage Li-metal batteries (LMBs). Whereas the fluorination of the ether backbone improves the oxidative stability, the resulting solvents lose their Li+ -solvation ability. Therefore, the rational molecular design of solvents is essential to combine high redox stability with good ionic conductivity. Here, we report the synthesis of a new high-voltage fluorinated ether solvent through integrated ring-chain molecular design, which can be used as a single solvent while retaining high-voltage stability. The controlled Li+ -solvation environment even at low-salt-concentration (1â M or 2â M) enables a uniform and compact Li anode and an outstanding cycling stability in the Li|NCM811 full cell (20â µm Li foil, N/P ratio of 4). These results show the impact of molecular design of electrolytes towards the utilization of LMBs.
Tetraoxa[8]circulenes (TOCs) are a class of hetero[8]circulenes featuring a planar cyclooctatetraene core with a mixed aromatic/antiaromatic motif that governs their electronic properties. Polymeric TOCs (pTOCs) have been the subject of several computational simulations because they are predicted to be low-band-gap semiconductors, but they have not been available synthetically yet. Here, we report the first example of pTOCs, a new family of porous semiconductors, synthesized under ionothermal conditions through the intermolecular cyclization of 1,4,5,8-anthracene tetrone. pTOCs are porous, with surface areas up to 1656â m2 g-1 , and exhibit light-switchable and tunable semiconducting properties.
Porous graphene membranes have emerged as promising alternatives for gas-separation applications due to their atomic thickness enabling ultrahigh permeance, but they suffer from low gas selectivity. Whereas decreasing the pore size below 3 nm is expected to increase the gas selectivity due to molecular sieving, it is rather challenging to generate a large number of uniform small pores on the graphene surface. Here, a pore-narrowing approach via gold deposition onto porous graphene surface is introduced to tune the pore size and thickness of the membrane to achieve a large number of small pores. Through the systematic approach, the ideal combination is determined as pore size below 3 nm, obtained at the thickness of 100 nm, to attain high selectivity and high permeance. The resulting membrane shows a H2 /CO2 separation factor of 31.3 at H2 permeance of 2.23 × 105 GPU (1 GPU = 3.35 × 10-10 mol s-1 m-2 Pa-1 ), which is the highest value reported to date in the 105 GPU permeance range. This result is explained by comparing the predicted binding energies of gas molecules with the Au surface, -5.3 versus -21 kJ mol-1 for H2 and CO2 , respectively, increased surface-gas interactions and molecular-sieving effect with decreasing pore size.
