Cluster Ions Research Articles

Thin Zinc Electrodes Stabilized with Organobromine‐Partnered H2O−Zn−MeOH Cluster Ions for Practical Zinc‐Metal Pouch Cells

AbstractThe utilization of thin zinc (Zn) anodes with a high depth of discharge is an effective strategy to increase the energy density of aqueous Zn metal batteries (ZMBs), but challenged by the poor reversibility of Zn electrode due to the serious Zn‐consuming side reactions at the Zn||electrolyte interface. Here, we introduce 2‐bromomethyl‐1,3‐dioxolane (BDOL) and methanol (MeOH) as electrolyte additive into aqueous ZnSO4 electrolyte. In the as‐formulated electrolyte, BDOL with a strong electron‐withdrawing group (−CH2Br) tends to pair with the H2O−Zn−MeOH complex, leading to the formation of organobromine‐partnered H2O−Zn−MeOH cluster ions. During the Zn electrodeposition process, the formed ZnO‐dominated by‐products induce the polymerization of BDOL monomers, which are previously adsorbed on the electrode. As a result, a uniform dual‐layer SEI with ZnO‐dominated outer layer and polyether‐dominated inner layer is built on the surface of Zn electrode. With such an in situ formed dual‐layer SEI, the Zn||Mg0.9Mn3O7 ⋅ 2.7H2O pouch cell using a 10‐um Zn anode (corresponding to a low negative to positive areal capacity ratio of 3.56) successfully operated for 300 cycles with a high capacity retention of 86 %, promising a high practical energy density of >120 Wh/kg (based on the total mass of Zn and Mg0.9Mn3O7 ⋅ 2.7H2O).

High-Performance Solid-State Lithium Metal Batteries of Garnet/Polymer Composite Thin-Film Electrolyte with Domain-Limited Ion Transport Pathways.

The integrated approach of interfacial engineering and composite electrolytes is crucial for the market application of Li metal batteries (LMBs). A 22 μm thin-film type polymer/Li6.4La3Zr1.4Ta0.6O12 (LLZTO) composite solid-state electrolyte (LPCE) was designed that combines fast ion conduction and stable interfacial evolution, enhancing lithium metal interface stability and cycling performance. The ether-based molecular coordination groups/clusters formed by triethylene glycol dimethyl ether (TGDE) and anions facilitated the movement of Li+ between the polymer chain segments. These specific coordination clusters significantly "constrained" the interaction between anions and Li+, inducing the anions to follow the clusters to the Li metal and preferentially participate in solid electrolyte interface (SEI) derivatization. The inorganic salt-rich gradient SEI modulates Li+ deposition and inhibits uncontrolled dendrite growth, achieving stable cycling of Li symmetric cell at 0.2 mA cm-2 for over 2000 h. Furthermore, the Li||NCM811 cell at a rate of 0.1 C exhibits an initial discharge capacity of 194.5 mAh g-1, maintaining a capacity retention rate of over 90% after 500 cycles. This work demonstrates the importance of domain-limited ion clusters in ion transport and interfacial evolution, providing a perspective for solid-state LMBs.

High‐Entropy Electrolyte Driven by Multi‐Solvation Structures for Long‐Lifespan Aqueous Zinc Metal Pouch Cells

Aqueous zinc metal batteries (AZMBs) are promising for grid‐scale energy storage due to their low cost and high safety. However, poor stability and an unfavorable freezing point hinder their actual application. Herein, a ternary salts‐based high‐entropy electrolyte (HEE) composed of Zn0.2Na0.4Li0.4(ClO4)1.2·7H2O is proposed to address the above issues. The addition of perchlorate salts with different cations reduces the size of ion clusters, significantly increases the solvation structure species, and promotes the anion‐rich Zn2+ solvation structures, resulting in an enlarged electrochemical stability window, favorable viscosity and ionic conductivity, and low freezing point. Furthermore, characterization and calculations confirm that multiple types of solvation structures effectively increase the electrolyte entropy. As a consequence, the Zn/Zn symmetric cells in HEE can sustainably cycle for at least 1000 hours and 1500 hours under room and subzero temperatures, respectively. The Na0.33V2O5/Zn and polyaniline/Zn full cells can even last for 30000 and 20000 cycles without capacity decay at −20 °C, respectively. The pouch cells employing HEE deliver promising capacity and stability, even at high mass loading of active materials. This strategy of introducing multiple salts with different cations to construct a high‐entropy environment provides a facile approach for high‐performance and long‐lifespan AZMBs across a wide temperature range.

High-Entropy Electrolyte Driven by Multi-Solvation Structures for Long-Lifespan Aqueous Zinc Metal Pouch Cells.

Aqueous zinc metal batteries (AZMBs) are promising for grid-scale energy storage due to their low cost and high safety. However, poor stability and an unfavorable freezing point hinder their actual application. Herein, a ternary salts-based high-entropy electrolyte (HEE) composed of Zn0.2Na0.4Li0.4(ClO4)1.2·7H2O is proposed to address the above issues. The addition of perchlorate salts with different cations reduces the size of ion clusters, significantly increases the solvation structure species, and promotes the anion-rich Zn2+ solvation structures, resulting in an enlarged electrochemical stability window, favorable viscosity and ionic conductivity, and low freezing point. Furthermore, characterization and calculations confirm that multiple types of solvation structures effectively increase the electrolyte entropy. As a consequence, the Zn/Zn symmetric cells in HEE can sustainably cycle for at least 1000 hours and 1500 hours under room and subzero temperatures, respectively. The Na0.33V2O5/Zn and polyaniline/Zn full cells can even last for 30000 and 20000 cycles without capacity decay at -20 °C, respectively. The pouch cells employing HEE deliver promising capacity and stability, even at high mass loading of active materials. This strategy of introducing multiple salts with different cations to construct a high-entropy environment provides a facile approach for high-performance and long-lifespan AZMBs across a wide temperature range.

Delivery of cations (Mg2+, Al3+, Ga3+, Sn2+, Cr3+, Fe3+) into the cells by anthocyanins through Physico-chemical assessment: A molecular simulation study

Anthocyanins (ACNs) are secondary metabolites responsible for most of the red to purple pigmentation found in flowers, fruits, and leaves. Clusters of metal ions of Mg2+, Al3+, Ga3+, Sn2+, Cr3+, Fe3+ joined to ACNs in water media were studied for unraveling the color shifting of different complexes of these structures in the low ranges of pH. In this verdict, it has been studied the metallic cations diffusing of deprotonating for the anthocyanin (ACN) (B)-ring of Malvidin (Mal), Peonidin (Peo), Delphinidin (Del), Pet, and Cyanidin (Cya) in water. The difference of heat of formation (∆Hf) among clusters of metallic cations jointed to ACNs has been illustrated toward the double bonds and carbonyl groups by the chelation of (B)-ring for cyanidin, delphinidin and petunidin ACNs in two media of gas and water that explains the stability and color of [ACN-metallic cations] cluster chelation. The complexes of Ga3+ → Pet, Cr3+ → Pet, Mg2+ → Pet and Al3+ → Cya, Ga3+ → Cya, Mg2+ → Cya have indicated the maximum absorbance in the low concentration. The mechanism of cation-induced ACNs mainly depends on the location of active zones of functionalized O-atoms in ACN and divalent or trivalent cations characteristics. Regarding the obtained results, regular consumption of some vegetables and fruits, which are rich in ACN molecules, should be helpful to stop viral infectious by decreasing pathogenicity and propagation of viral diseases.

High-Entropy Multiple-Anion Aqueous Electrolytes for Long-Life Zn-Metal Anodes.

Aqueous zinc-ion batteries (AZIBs) hold great promise for large-scale energy storage applications, however, their practical use is significantly hindered by issues such as zinc dendrite growth and hydrogen evolution. To address these challenges, we propose a high-entropy (HE) electrolyte design strategy that incorporates multiple zinc salts, aimed at enhancing ion kinetics and improving the electrochemical stability of the electrolyte. The interactions between multiple anions and Zn2+ increase the complexity of the solvation structure, resulting in smaller ion clusters while maintaining weakly anion-rich solvation structures. This leads to improved ion mobility and the formation of robust interphase layers on the electrode-electrolyte interface. Moreover, the HE electrolyte effectively suppresses hydrogen evolution and corrosion side reactions while facilitating uniform and reversible Zn plating/stripping processes. Impressively, the optimized electrolyte enables dendrite-free Zn plating/stripping for over 3000 h in symmetric cells and achieves a high Coulombic efficiency of 99.5% at 10 mA cm-2 in asymmetric cells. Inspiringly, full cells paired with Ca-VO2 cathodes demonstrate excellent performance, retaining 81.5% of the initial capacity over 1800 cycles at 5 A g-1. These significant findings highlight the potential of this electrolyte design strategy to improve the performance and lifespan of Zn-metal anodes in AZIBs.

A small-molecule carrier for the intracellular delivery of a membrane-impermeable protein with retained bioactivity.

Intracellular protein delivery has the potential to revolutionize cell-biological research and medicinal therapy, with broad applications in bioimaging, disease treatment, and genome editing. Herein, we demonstrate successful delivery of a functional protein, cytochrome c (CYC), by using a boron cluster anion as molecular carrier of the superchaotropic anion type (B12Br11OPr2-). CYC was delivered into lipid bilayer vesicles as well as living cells, with a cellular uptake ratio approaching 90%. Mechanistic studies showed that CYC was internalized into cells through a permeation pathway directly into the cytoplasm, bypassing endosomal entrapment. Upon carrier-assisted internalization, CYC retained its bioactivity, as reflected by an induced cell apoptosis rate of 25% at low dose (1 µM). This study furbishes a direct protein delivery method by a molecular carrier with high efficiency, confirming the potential of inorganic cluster ions as protein transport vehicles with an extensive range of future cell-biological or biomedical applications.

A multi-domain snail metallothionein increases cadmium resistance and fitness in Caenorhabditis elegans

Metallothioneins (MTs) are a family of mostly low-molecular weight, cysteine-rich proteins capable of specific metal-ion binding that are involved in metal detoxification and homeostasis, as well as in stress response. In contrast to most other animal species which possess two-domain (bidominial) MTs, some gastropod species have evolved Cd2+-selective multidomain MTs (md-MTs) consisting of several concatenated β3 domains and a single C-terminal β1 domain. Each domain contains three-metal ion clusters and binds three metal ions. The terrestrial snail Alinda biplicata possesses, among other MT isoforms, an md-MT with nine β3 domains and a C-terminal β1 domain (termed 10md-MT), capable of binding up to 30 Cd2+ ions per protein molecule. In the present study, the Alinda biplicata 10md-MT gene and a truncated version consisting of one β3 domain and a single C-terminal β1 domain (2d-MT) were introduced into a Caenorhabditis elegans knock-out strain lacking a native MT gene (mtl-1). The two snail MT constructs consistently increased Cd2+ resistance, and partially improved morphological, life history and physiological fitness traits in the nematode model host Caenorhabditis elegans. This highlights how the engineering of transgenic Caenorhabditis elegans strains expressing snail MTs provides an enhancement of the innate metal detoxification mechanism and in doing so provides a platform for enhanced mechanistic toxicology.

Mechanistic insights into uptake, transfer and exchange of metal ions by the three-metal clusters of a metalloprotein.

Metallothioneins (MTs) are small proteins that coordinate d-block metal ions in sulfur-metal clusters to control metal ion concentrations within the cell. Here we study metal cluster formation in the MT of the periwinkle Littorina littorea (LlMT) by nuclear magnetic resonance (NMR). We demonstrate that the three Cd2+ ions in each domain are taken up highly cooperatively, that is, in an all-or-none fashion, with a four- to six-fold higher affinity for the C-terminal domain. During the transfer of metal ions from Cd2+-loaded MT to apo MT, Cd2+ is most efficiently transferred from the metalated protein to the apo C-terminal domain. This behavior might be connected to unique structural motifs in the C-terminal domain, such as two double-CXC motifs and an increased proportion of positively charged residues. In Cd2+/Zn2+ metal exchange experiments, the N-terminal domain displayed the most efficient inter-molecular metal exchange. Amide hydrogen exchange reveals fewer protected amides for the N-terminal domain, suggesting the structure might more easily "open up" to facilitate metal exchange. Experiments with a physical separation of donor and acceptor species demonstrate that metal exchange and transfer require protein-protein contacts. These findings provide insights into the mechanism of metal uptake and metal transfer, which are important processes during metal detoxification in snail MTs.

Anomalous Pressure-Induced Blue-Shifted Emission of Ionic Copper-Iodine Clusters: The Competitive Effect between Cuprophilic Interactions and Through-Space Interactions.

Developing ionic copper-iodine clusters with multiple emitting is crucial for enriching lighting and display materials with various colors. However, the luminescent properties of traditional ionic copper-iodine clusters are often closely associated with low-energy cluster-centered triplet emission, which will redshift further as the Cu⋅⋅⋅Cu bond length decreases. This article utilizes a pressure-treated strategy to achieve an anomalous pressure-induced blue-shifted luminescence phenomenon in ionic Cu4I6(4-dimethylamino-1-ethylpyridinium)2 crystals for the first time, which is based on dominant through-space charge-transfer (TSCT). Herein, we reveal that the more advantageous through-space interactions in the competition between cuprophilic interactions and through-space interactions can lead to a blue-shifted luminescence. High-pressure angle-dispersive X-ray diffraction and high-pressure infrared experiments show that the enhanced through-space interactions mainly originate from forming new intermolecular C-H⋅⋅⋅I hydrogen bonds and the enhancement of van der Waals interactions between organic cations and anionic clusters. Theoretical calculations and experimental studies of excited-state dynamics confirm that the blue-shifted emission is due to the increased energy gap between the excited triplet and ground states caused by the electron delocalization under stronger through-space interactions. This work deepens previous understanding and provides a new avenue to design and synthetic ionic copper-iodine clusters with high-energy TSCT emission.

Effects of Hydrogen Dissociation During Gas Flooding on Formation of Metal Hydride Cluster Ions in Secondary Ion Mass Spectrometry.

The application of hydrogen flooding was recently shown to be a simple and effective approach for improved layer differentiation and interface determination during secondary ion mass spectrometry (SIMS) depth profiling of thin films, as well as an approach with potential in the field of quantitative SIMS analyses. To study the effects of hydrogen further, flooding of H2 molecules was compared to reactions with atomic H on samples of pure metals and their alloys. H2 was introduced into the analytical chamber via a capillary, which was heated to approximately 2200 K to achieve dissociation. Dissociation of H2 up to 30% resulted in a significant increase in the intensity of the metal hydride cluster secondary ions originating from the metallic samples. Comparison of the time scales of possible processes provided insight into the mechanism of hydride cluster secondary ion formation. Cluster ions presumably form during the recombination of the atoms and molecules from the sample and atoms and molecules adsorbed from the gas. This process occurs on the surface or just above it during the sputtering process. These findings coincide with those of previous mechanistic and computational studies.

Construction and Evaluation of pH‐Responsive Nitrogen‐Containing Metal–Organic Frameworks as Oral Drug Carriers

ABSTRACTMetal–organic framework (MOF) is a porous material composed of metal ions/clusters and organic ligands. It has attracted much attention due to its high specific surface area, good biocompatibility, chemical modifiability, and diversity of components. Among many MOFs, zirconium‐based MOFs are particularly suitable for biological applications due to their optimal stability and low toxicity to hydrolysis. However, due to the weak coordination bonds between many metal clusters and organic ligands, most MOFs are prone to collapse in acidic environments, and the stability of MOFs as drug carriers cannot be guaranteed so that they cannot be widely used as oral drug carriers. This study synthesized the three MOFs using metal Zr ion clusters as the center and different nitrogen‐containing organic ligands, which are stable in gastric acid, namely, UiO‐66‐PDC, UiO‐66‐NH2, and UiO‐66‐NO2. The anionic drug loxoprofen (LOX) was loaded and characterized using scanning electron microscopy, infrared spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and x‐ray diffraction. The adsorption and release behaviors of LOX and the three MOFs were studied from the molecular point of view by computer simulation. A series of behaviors and mechanisms of pH‐responsive nitrogen‐containing MOFs as oral drug carriers were further explored through rat pharmacokinetic experiments, the everted gut sac experiments, and intestinal absorption mechanism experiments. The experimental results show that there is a strong electrostatic interaction between anionic drug LOX and UiO‐66‐PDC under simulated gastric acid environment, which prolongs the half‐life of the drug, proving that LOX@UiO‐66‐PDC is a promising new oral drug delivery system.

2M NaCl by XPS using monochromatic Al K α x rays

Cryo-XPS enables the study of many substances that are unsuitable for standard XPS analysis, such as moderately volatile liquids, biological samples, porous materials, and polymeric materials that may outgas significantly under ultrahigh vacuum conditions. In this article, XPS spectra of a 50 μl frozen droplet of 2M sodium chloride solution (NaCl) in Millipore water purified to 18.2 MΩ cm at 25 °C were obtained using an Al Kα (1486.6 eV) source with a quartz (1010) crystal monochromator through first order diffraction and irradiating the sample at 54.7° to the surface normal. The sample was sputter cleaned using a Gas Cluster Ion Source pre-acquisition to remove the minor layer of adventitious carbon contamination on the surface. Spectra of the principal lines include Na 1s, O 1s, and Cl 2p. Spectra of O KLL, Na KLL, Cl 2s, Na 2s, Na 2p, O 2s, and valence band were also acquired.

Enhanced 3 μm emission in Ho3+/Yb3+ co-doped bismuth-fluoride glasses by Gd2O3

In this work, (100-b)(45Bi2O3-40GeO2-15BaF2)-bGd2O3-2Yb2O3-0.5Ho2O3 glass was prepared to use a high-temperature melting method(where b= 0, 2.5, 5, 7.5, 10). The absorption and fluorescence spectra indicate that the optimal Gd2O3 content is 7.5 mol% (BGBG7.5HY), with an Ω2 value of 6.20×10−20 cm2 for the main glass, which is superior to that of BGBG0HY glass. This suggests that the incorporation of Gd2O3 enhances the mid-infrared emission capacity. Raman spectroscopy studies demonstrate that the introduction of Gd₂O₃ results in a substantial influx of oxygen atoms into the glass network, accompanied by a transition of [BiO₆] to [BiO₃] within the glass mesh. This is evidenced by a notable redshift of the characteristic peaks at 509 cm−1 and 677 cm−1 in comparison to BGB glass. The introduction of Gd2O3 also expands the distance between Ho3+/Yb3+ ions, inhibits rare earth ion clusters, improves the Ho3+ luminescence center environment, and thus enhances the 3 μm emission performance of bismuth fluoride glass. The maximum emission cross section is 1.82 × 10−20 cm2 and the maximum gain coefficient is 3.71 cm−1. The results show that the bismuth fluoride glass prepared in this paper is an excellent gain material for mid-infrared fiber lasers.

Ion Clusters Boost Extensional Flow-Induced Crystallization in Ionomers

Ion Clusters Boost Extensional Flow-Induced Crystallization in Ionomers

On the potential of the Cluster Ion Counter (CIC) to observe local new particle formation, condensation sink and growth rate of newly formed particles

Abstract. The Cluster Ion Counter (CIC) is a simple three-channel instrument designed to observe ions in the electrical mobility equivalent diameter range from 1.0 to 5 nm. With the three channels, we can observe concentrations of both ion clusters (sub-2 nm ions) and intermediate ions. Furthermore, as derived here, we can estimate condensation sink (CS), intensity of local new particle formation, growth rate of newly formed particles from 2 to 3 nm and formation rate of 2 nm ions. We compared CIC measurements with those of a multichannel ion spectrometer, the Neutral cluster and Air Ion Spectrometer (NAIS), and found that the concentrations agreed well between the two instruments, with correlation coefficients of 0.89 and 0.86 for sub-2 nm and 2.0–2.3 nm ions, respectively. According to the observations made in Hyytiälä, Finland, and Beijing, China, the ion source rate was estimated to be about two to four ion pairs cm−3 s−1. The new CIC is a simple and cheap instrument that can be used in different environments to obtain information about small ion dynamics, local intermediate ion formation and CS in a robust way when combined with the theoretical framework presented here.

Thin Zinc Electrodes Stabilized with Organobromine-Partnered H2O-Zn-MeOH Cluster Ions for Practical Zinc-Metal Pouch Cells.

The utilization of thin zinc (Zn) anodes with a high depth of discharge is an effective strategy to increase the energy density of aqueous Zn metal batteries (ZMBs), but challenged by the poor reversibility of Zn electrode due to the serious Zn-consuming side reactions at the Zn||electrolyte interface. Here, we introduce 2-bromomethyl-1,3-dioxolane (BDOL) and methanol (MeOH) as electrolyte additive into aqueous ZnSO4 electrolyte. In the as-formulated electrolyte, BDOL with a strong electron-withdrawing group (-CH2Br) tends to pair with the H2O-Zn-MeOH complex, leading to the formation of organobromine-partnered H2O-Zn-MeOH cluster ions. During the Zn electrodeposition process, the formed ZnO-dominated by-products induce the polymerization of BDOL monomers, which are previously adsorbed on the electrode. As a result, a uniform dual-layer SEI with ZnO-dominated outer layer and polyether-dominated inner layer is built on the surface of Zn electrode. With such an in-situ formed dual-layer SEI, the Zn||Mg0.9Mn3O7·2.7H2O pouch cell using a 10-um Zn anode (corresponding to a low negative to positive areal capacity ratio of 3.56) successfully operated for 300 cycles with a high capacity retention of 86%, promising a high practical energy density of > 120 Wh/kg (based on the total mass of Zn and Mg0.9Mn3O7·2.7H2O).

Generation-fusion strategy in metal-earth ionosome investigation using single-entity electrochemistry at the micro-water/trifluorotoluene interface

Ionosomes are water clusters/droplets formed in an organic phase via the spontaneous assembly of ionic bilayers by hydrated cations or anions. The ionosomes formed by monovalent ions, i.e., Li+, Na+, K+, Cl−, etc., have been thoroughly investigated. Herein, single nanowater clusters (viz. ionosomes) in organic solutions, which are formed by the transfer of metal earth cations (i.e., Mg2+, Ca2+, Ba2+) into organic lipophilic electrolytes, were discovered using single-entity electrochemistry (SEE). The generation-fusion strategy involving two-step potentiostatic chronoamperometry was applied to investigate single Mg2+-ionosomes at the water/α,α,α-trifluorotoluene (w/TFT) interface. After an exciting potential forced the hydrophilic ion into the organic phase, a train of current spikes with information on the integrated charges, frequency, and duration were recorded to gain insight into the ionosomes. Variates were thoroughly investigated, including the exciting potential, exciting time, recording potential, size of the applied w/TFT interface, ion species, and concentration. These results suggest that: (1) the size of a single Mg2+-ionosome was revealed; (2) the fleshly formed ionosomes are mainly located on the organic side of the w/TFT interfacial surface instead of diffusing into the organic bulk; (3) when the interface decreases, fewer ionosomes form, and the size of the ionosomes decreases; (4) the mean charge carried by a single ionosome is positively related to the charge density of a single cation; (5) by alternating the recording potential, the negative zeta potential of Mg2+-ionosomes was revealed; (6) Mg2+-ionosomes can form when the aqueous solution contains only 2 μmol·L−1 Mg2+. This work thoroughly investigated hydrated metal earth ion clusters in the organic phase via SEE and provides insights into the interface electric double layer from the electrochemistry perspective. In addition to promoting the understanding of ionosomes, this strategy can provide potential applications to identify high-purity water.

Effect of succinonitrile on the structural, ion conductivity, and dielectric properties of PVDF‐HFP based solid polymer electrolytes

AbstractA detailed account of the poly(vinylidene difluoride‐co‐hexafluoropropylene) (PVDF‐HFP)/succinonitrile (SN)/lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) based solid polymer electrolytes (SPEs) of various compositions is reported. SN is incorporated as plasticizer, while LiTFSI is employed as the source of lithium ions. Fourier transfer infrared (FTIR) spectroscopy reveals the formation of polar and electroactive γ crystal phase by PVDF in pristine PVDF‐HFP and the prepared SPE films. FTIR further confirms the interaction between the host polymer and the salt and between the salt and the plasticizer. The interaction between the salt and plasticizer suggests that SN not only offers the plasticization effect but also facilitates salt dissociation. The ion conductivity increases with increasing salt content up to 20 wt% but beyond that concentration a decline in ion conductivity is observed, which could be attributed to the ion pair association or cluster formation due to the excess salt concentration that reduces the availability of free ions and ultimately leads to the reduction in ion conductivity. After including SN in the SPE formulation, electrochemical impedance spectroscopy reveals a substantial increase in room temperature ion conductivity of the SPE from ~1.08 × 10−5 S cm−1 for pristine SPE with 20 wt% salt to ~2.7 × 10−4 S cm−1 for plasticized SPE with 40 wt% SN and 20 wt% salt. This is attributed to the plasticizing effect of SN that enhances ion mobility through the matrix and to the increased charge carrier concentration (SN facilities salt dissociation). The fabricated SPEs exhibit a significant enhancement in ion conductivity with increasing temperature and the maximum ion conductivity of 1.1 × 10−3 S cm−1 is attained at 393 K by plasticized SPE with 40 wt% SN content. The ion conductivity of all the prepared SPEs follows the temperature dependent Arrhenius behavior, suggesting the thermally activated ion hopping mechanism of ionic conduction. Further, the plasticized SPEs display near unity ion transference number indicating the predominance of the ionic mode of conduction. The dielectric and electric modulus analysis reveal a faster relaxation phenomenon and hence higher ion conductivity of the prepared SPEs with increasing salt and plasticizer content.

Research on microscopic structure–activity relationship of AP particle–matrix interface in HTPB propellant

Abstract The matrix and particle interface of hydroxyl-terminated polybutadiene (HTPB) propellant is the weakest part of its mechanical properties, making it prone to dewetting damage and destroying the structural integrity of the propellant. This article uses nano-indentation, gas cluster ion beam etching, and X-ray photoelectron spectroscopy experimental analyses to study the physicochemical properties of the interface and subsequently construct a microscopic model for the HTPB matrix and ammonium perchlorate particle interface. The model fully considers the existing forms of curing agent toluene diisocyanate, bonding agent Tris (2-methyl-aziridine) phosphine oxide (MAPO), and the aging products of the propellant in the interface structure. Meanwhile, the physicochemical properties, mechanical properties, and adhesive properties of the interface under different tensile loading conditions were analyzed. The results indicate that the bonding agent MAPO significantly enhances the mechanical and adhesive properties of the interface. The interface is sensitive to changes in temperature and tensile rate, and the aged interface is more fragile.