Separation of iodate, bromide, nitrite, nitrate, and iodide in seawater by ion chromatography using 1-aminoundecyl group chemically bonded silica columns.

The separation and detection of six common inorganic anions (iodate (IO3-), bromate (BrO3-), bromide (Br-), nitrite (NO2-), nitrate (NO3-), and iodide (I-)) in pure water and 35 ‰ artificial seawater were examined by ion chromatography (IC). As packing materials of separation columns, 1-aminoundecyl group chemically bonded silica (AUS) gels were prepared. Separation of the anions in pure water was achieved using separation columns (150 mm × 4.6 mm i.d.) packed with the AUS gels, 0.1 M NaCl + 5 mM phosphate buffer (pH 4.5) as eluent, and a UV detector (wavelength 225 nm). The anions in artificial seawater were separated and detected with a 300 mm-long column without interferences by matrix anions such as chloride (Cl-) and sulfate (SO42-). The stationary phases have high-capacity anion-exchange/hydrophilic/hydrophobic interaction mixed-modes. The IC system was applied to five inorganic anions, IO3-, Br-, NO2-, NO3-, and I- in seawater of the Seto-Inland Sea, Japan. The detection limits (DLs, S/N = 3) were 11 µg L-1 (IO3-), 93 (Br-), 1.3 (NO2-), 1.4 (NO3-), and 1.1 (I-) for a 100-µL sample injection.

Regulating the zinc ion transport kinetics of Mn3O4 through copper doping towards high-capacity aqueous Zn-ion battery.

High working voltage, large theoretical capacity and cheapness render Mn3O4 promising cathode candidate for aqueous zinc ion batteries (AZIBs). Unfortunately, poor electrochemical activity and bad structural stability lead to low capacity and unsatisfactory cycling performance. Herein, Mn3O4 material was fabricated through a facile precipitation reaction and divalent copper ions were introduced into the crystal framework, and ultra-small Cu-doped Mn3O4 nanocrystalline cathode materials with mixed valence states of Mn2+, Mn3+ and Mn4+ were obtained via post-calcination. The presence of Cu acts as structural stabilizer by partial substitution of Mn, as well as enhance the conductivity and reactivity of Mn3O4. Significantly, based on electrochemical investigations and ex-situ XPS characterization, a synergistic effect between copper and manganese was revealed in the Cu-doped Mn3O4, in which divalent Cu2+ can catalyze the transformation of Mn3+ and Mn4+ to divalent Mn2+, accompanied by the translation of Cu2+ to Cu0 and Cu+. Benefitting from the above advantages, the Mn3O4 cathode doped with moderate copper (abbreviated as CMO-2) delivers large discharge capacity of 352.9 mAh g-1 at 100 mA g-1, which is significantly better than Mn3O4 (only 247.8 mAh g-1). In addition, CMO-2 holds 203.3 mAh g-1 discharge capacity after 1000 cycles at 1 A g-1 with 98.6 % retention, and after 1000 cycles at 5 A g-1, it still performs decent discharge capacity of 104.2 mAh g-1. This work provides new ideas and approaches for constructing manganese-based AZIBs with long lifespan and high capacity.

Optimization of headspace high-capacity tool coupled to two-dimensional gas chromatography-mass spectrometry for mapping the volatile organic compounds of raw pistachios. A proof-of-concept on the classification ability by geographic origin.

An optimized procedure for extracting and analyzing raw pistachio volatiles was developed through headspace sampling with high-capacity tools and subsequent analysis using comprehensive two-dimensional gas chromatography coupled with mass spectrometry. The examination of 18 pistachio samples belonging to different geographic areas led to the identification of a set of 99 volatile organic compounds (VOCs). Molecules were putatively identified using linear retention index, mass spectra similarity, and two-dimensional plot location. The impact of preprocessing and processing techniques on the aligned data matrix from a set of samples of different geographical origins, after removing contaminants, was evaluated. The combination of scaling with log-transformation, normalization with z-score, and data reduction with random forest machine learning algorithm generated a panel of 16 discriminatory VOC molecules. As a proof of concept, raw pistachios' VOC profile was employed for the first time to tentatively classify them based on their geographical origin.

Planar Zn-Ion Microcapacitors with High-Capacity Activated Carbon Anode and VO2 (B) Cathode.

The downsizing of microscale energy storage devices plays a crucial role in powering modern emerging devices. Therefore, the scientific focus on developing high-performance microdevices, balancing energy density and power density, becomes essential. In this context, we explore an advanced Microplotter technique to fabricate hybrid planar Zn-ion microcapacitors (ZIMCs) that exhibit dual charge storage characteristics, with an electrical double layer capacitor type activated carbon anode and a battery type VO2 (B) cathode, aiming to achieve energy density surpassing supercapacitors and power density exceeding batteries. Effective loading of VO2 (B) cathode electrode materials combined with activated carbon anode onto confined planar microelectrodes not only provides reversible Zn2+ storage performance but also mitigates dendrite formation. This not only results in superior charge storage performance, including areal energies of 2.34 µWh/cm2 (at 74.76 µW/cm2) and 0.94 µWh/cm2 (at 753.12 µW/cm2), exceeding performance of zinc nanoparticle anode and activated carbon cathode based ZIMCs, but also ensures stable capacity retention of 87% even after 1000 cycles and free from any unwanted dendrites. Consequently, this approach is directed toward the development of high-performance ZIMCs by exploring high-capacity materials for efficient utilization on microelectrodes and achieving maximum possible capacities within the constraints of the limited device footprint.

Extending the π-Conjugation of A Donor-Acceptor Covalent Organic Framework for High-Rate and High-Capacity Lithium-Ion Batteries.

Realizing high-rate and high-capacity features of Lihium-organic batteries is essential for their practical use but remains a big challenge, which is due to the instrinsic poor conductivity, limited redox kinetics and low utility of organic electrode mateials. This work presents a well-designed donor-acceptor Covalent Organic Framework (COFs) with extended conjugation, mesoscale porosity, and dual redox-active centers to promote fast charge transfer and multi-electron processes. As anticipated, the prepared cathode with benzo [1,2-b:3,4-b':5,6-b''] trithiophene (BTT) as p-type and pyrene-4,5,9,10-tetraone (PTO) as n-type material (BTT-PTO-COF) delivers impressive specific capacity (218 mAh g-1 and 275 mAh g-1 at 0.2 A g-1 in ether-based and carbonate-based electrolyte respectively) and outstanding rate capability (79 mAh g-1 at 50 A g-1 in ether-based electrolyte and 124 mAh g-1 at 10 A g-1 in carbonate-based electrolyte). Moreover, the potential of BTT-PTO-COF electrode for prototype batteries has been demonstrated by full cells of dual-ion batteries, which attain comparable electrochemical performances to the half cells. Moreover, mechanism studies combining ex-situ characterization and theoratical calculations reveal the efficient dual-ion storage process and facile charge transfer of BTT-PTO-COF. This work not only expands the diversity of redox-active COFs but also provide concept of structure design for high-rate and high-capacity organic electrodes.

Perspective on Lewis Acid-Base Interactions in Emerging Batteries.

Lewis acid-base interactions are common in chemical processes presented in diverse applications, such as synthesis, catalysis, batteries, semiconductors, and solar cells. The Lewis acid-base interactions allow precise tuning of material properties from the molecular level to more aggregated and organized structures. This review will focus on the origin, development, and prospects of applying Lewis acid-base interactions for the materials design and mechanism understanding in the advancement of battery materials and chemistries. The covered topics relate to aqueous batteries, lithium-ion batteries, solid-state batteries, alkali metal-sulfur batteries, and alkali metal-oxygen batteries. In this review, the Lewis acid-base theories will be first introduced. Thereafter the application strategies for Lewis acid-base interactions in solid-state and liquid-based batteries will be introduced from the aspects of liquid electrolyte, solid polymer electrolyte, metal anodes, and high-capacity cathodes. The underlying mechanism is highlighted in regard to ion transport, electrochemical stability, mechanical property, reaction kinetics, dendrite growth, corrosion, and so on. Last but not least, perspectives on the future directions related to Lewis acid-base interactions for next-generation batteries are like to be shared.

Enhancing Reversibility and Kinetics of Anionic Redox in O3-NaLi1/3Mn2/3O2 through Controlled P2 Intergrowth.

Anionic redox chemistry can surpass theoretical limits of conventional layered oxide cathodes in energy density. A recent model system of sodium-ion batteries, O3-NaLi1/3Mn2/3O2, demonstrated full anionic redox capacity but is limited in reversibility and kinetics due to irreversible structural rearrangement and oxygen loss. Solutions to these issues are missing due to the challenging synthesis. Here, we harness the unique structural richness of sodium layered oxides and realize a controlled ratio of P2 structural intergrowth in this model compound with the overall composition maintained. The resulted O3 with 27% P2 intergrowth structure delivers an excellent initial Coulombic efficiency of 87%, comparable to the state-of-the-art Li-rich NMCs. This improvement is attributed to the effective suppression of irreversible oxygen release and structural changes, evidenced by operando Differential Electrochemical Mass Spectroscopy and X-ray Diffraction. The as-prepared intergrowth material, based on the environmentally benign Mn, exhibits a reversible capacity of 226 mAh g-1 at C/20 rate with excellent cycling stability stemming from the redox reactions of oxygen and manganese. Our work isolates the role of P2 structural intergrowth and thereby introduces a novel strategy to enhance the reversibility and kinetics of anionic redox reactions in sodium layered cathodes without compromising capacity.

Construction and Characterization of a High-Capacity Replication-Competent Murine Cytomegalovirus Vector for Gene Delivery.

We investigated the basic characteristics of a new murine cytomegalovirus (MCMV) vector platform. Using BAC technology, we engineered replication-competent recombinant MCMVs with deletions of up to 26% of the wild-type genome. To this end, we targeted five gene blocks (m01-m17, m106-m109, m129-m141, m144-m158, and m159-m170). BACs featuring deletions from 18% to 26% of the wild-type genome exhibited delayed virus reconstitution, while smaller deletions (up to 16%) demonstrated reconstitution kinetics similar to those of the wild type. Utilizing an innovative methodology, we introduced large genomic DNA segments, up to 35 kbp, along with reporter genes into a newly designed vector with a potential cloning capacity of 46 kbp (Q4). Surprisingly, the insertion of diverse foreign DNAs alleviated the delayed plaque formation phenotype of Q4, and these large inserts remained stable through serial in vitro passages. With reporter-gene-expressing recombinant MCMVs, we successfully transduced not only mouse cell lines but also non-rodent mammalian cells, including those of human, monkey, bovine, and bat origin. Remarkably, even non-mammalian cell lines derived from chickens exhibited successful transduction.

Enhancing Proton Co-Intercalation in Iron Ion Batteries Cathodes for Increased Capacity.

Recently, aqueous iron ion batteries (AIIBs) using iron metal anodes have gained traction in the battery community as low-cost and sustainable solutions for green energy storage. However, the development of AIIBs is significantly hindered by the limited capacity of existing cathode materials and the poor intercalation kinetic of Fe2+. Herein, we propose a H+ and Fe2+ co-intercalation electrochemistry in AIIBs to boost the capacity and rate capability of cathode materials such as iron hexacyanoferrate (FeHCF) and Na4Fe3(PO4)2(P2O7) (NFPP). This is achieved through an electrochemical activation step during which a FeOOH nanowire layer is formed in situ on the cathode. This layer facilitates H+ co-intercalation in AIIBs, resulting in a high specific capacity of 151 mAh g-1 and 93% capacity retention over 500 cycles for activated FeHCF cathodes. We found that this activation process can also be applied to other cathode chemistries, such as NFPP, where we found that the cathode capacity is doubled as a result of this process. Overall, the proposed H+/Fe2+ co-insertion electrochemistry expands the range of applications for AIBBs, in particular as a sustainable solution for storing renewable energy.

Interface-Engineered Atomic Layer Deposition of 3D Li4Ti5O12 for High-Capacity Lithium-Ion 3D Thin-Film Batteries.

Upcoming energy-autonomous mm-scale Internet-of-things devices require high-energy and high-power microbatteries. On-chip 3D thin-film batteries (TFBs) are the most promising option but lack high-rate anode materials. Here, Li4Ti5O12 thin films fabricated by atomic layer deposition (ALD) are electrochemically evaluated on 3D substrates for the first time. The 3D Li4Ti5O12 reveals an excellent footprint capacity of 20.23 µAh cm-2 at 1 C. The outstanding high-rate capability is demonstrated with 7.75 µAh cm-2 at 5 mA cm-2 (250 C) while preserving a remarkable capacity retention of 97.4% after 500 cycles. Planar films with various thicknesses exhibit electrochemical nanoscale effects and are tuned to maximize performance. The developed ALD process enables conformal high-quality spinel (111)-textured Li4Ti5O12 films on Si substrates with an area enhancement of 9. Interface engineering by employing ultrathin AlOx on the current collector facilitates a required crystallization time reduction which ensures high film and interface quality and prospective on-chip integration. This work demonstrates that 3D Li4Ti5O12 by ALD can be an attractive solution for the microelectronics-compatible fabrication of scalable high-energy and high-power Li-ion 3D TFBs.

Amorphous GeSnSe nanoparticles as a Li-Ion battery anode with High-Capacity and long cycle performance.

A new ternary amorphous GeSnSe (GSS) nanopowder was effectively synthesized by using ball milling under inert atmosphere. Its topographical, microstructural and elemental characterizations revealed the formation of nanoparticles with undefined shape, short-range order and the tailored stoichiometry. Remarkably, this novel amorphous material demonstrates its competences as a promising Li-ion host anode, exhibiting a high cycle performance with a specific charge capacity of 963 mAh g-1 at an applied C-rate of 0.2C with a coulombic efficiency > 99.4 % after 300 cycles. Its high specific capacity, large rate capability, acceptable capacity retention and long cycle life could be attributed to a dual Li-ion storage mechanism that consists mostly of multiple reversible electrochemical processes as conversion and alloying reactions and capacitive processes. Moreover, its stable volume expansion (34 %), moderate electrode polarization (248.9 mV), reasonable charge transfer resistance (83 Ω) and apparent Li-ion diffusion coefficients between 10-9 - 10-14 cm2 s-1 could be promoted by a synergistic effect between Ge (capacity), Sn (conductivity) and Se (stability), which plays an important role on the stability and high cycle performance of the promising GSS-based anode.

Low-Surface-Area Nitrogen-Doped Carbon Submicrospheres as High-Coulombic-Efficiency and High-Capacity Anodes for Practical Sodium-Ion Batteries.

Nitrogen-doped carbon submicrospheres (NCSMs) are synthesized via an efficient and environmentally friendly one-pot polymerization reaction at room temperature, in which dopamine hydrochloride serves as the source for both carbon and nitrogen. Through leverage of its distinctive structure characterized by minimal surface area, fewer oxygen-containing functional groups, and a heightened presence of active nitrogen-doping sites, the synthesized NCSM showcases a noteworthy initial Coulombic efficiency (ICE) of 84.8%, a remarkable sodium storage capacity of 384 mAh g-1, an impressive rate capability of 215 mAh g-1 at 10 A g-1, and a superior cyclic performance, maintaining 83.0% of its capacity after 2000 cycles. The submicron spherical structure, with its limited surface area and scarce oxygen-containing moieties, effectively curtails the irreversible sodium-ion loss in solid-electrolyte interphase film formation, resulting in heightened ICE. The abundant nitrogen doping can expand carbon-layer spacing as well as improve the electron/ion-transport dynamics, guaranteeing a high sodium storage capacity and a strong rate capability. Crucially, the synthesis method presented here is straightforward, effective, and amenable to scaling, offering a novel avenue for the commercialization of sodium-ion batteries.

Controllable Design of Metal-Organic Framework-Derived Vanadium Oxynitride for High-Capacity and Long-Cycle Aqueous Zn-Ion Batteries.

Introducing N atoms in vanadium oxides (VOx) of aqueous Zn-ion batteries (ZIBs) can reduce their bandgap energy and enhance their electronic conductivity, thereby promoting the diffusion of Zn2+. The close-packed vanadium oxynitride (VON) generated often necessitates the intercalation of water molecules for restructuring, rendering it more conducive for zinc ion intercalation. However, its dense structure often causes structural strain and the formation of by-products during this process, resulting in decreased electrochemical performance. Herein, carbon-coated porous V2O3/VN nanosheets (p-VON@C) are constructed by annealing vanadium metal-organic framework in an ammonia-contained environment. The designed p-VON@C nanosheets are efficiently converted to low-crystalline hydrated N-doped VOx during subsequent activation while maintaining structural stability. This is because the V2O3/VN heterojunction and abundant oxygen vacancies in p-VON@C alleviate the structural strain during water molecule intercalation, and accelerate the intercalation rate. Carbon coating is beneficial to prevent p-VON@C from sliding or falling off during the activation and cycling process. Profiting from these advantages, the activated p-VON@C cathode delivers a high specific capacity of 518 mAh g-1 at 0.2 A g-1 and maintains a capacity retention rate of 80.9% after 2000 cycles at 10 A g-1. This work provides a pathway to designing high-quality aqueous ZIB cathodes.

Engineering a Low-Strain Si@TiSi2@NC Composite for High-Performance Lithium-Ion Batteries.

The huge volume expansion/contraction of silicon (Si) during the lithium (Li) insertion/extraction process, which can lead to cracking and pulverization, poses a substantial impediment to its practical implementation in lithium-ion batteries (LIBs). The development of low-strain Si-based composite materials is imperative to address the challenges associated with Si anodes. In this study, we have engineered a TiSi2 interface on the surface of Si particles via a high-temperature calcination process, followed by the introduction of an outermost carbon (C) shell, leading to the construction of a low-strain and highly stable Si@TiSi2@NC composite. The robust TiSi2 interface not only enhances electrical and ionic transport but also, more critically, significantly mitigates particle cracking by restraining the stress/strain induced by volumetric variations, thus alleviating pulverization during the lithiation/delithiation process. As a result, the as-fabricated Si@TiSi2@NC electrode exhibits a high initial reversible capacity (2172.7 mAh g-1 at 0.2 A g-1), superior rate performance (1198.4 mAh g-1 at 2.0 A g-1), and excellent long-term cycling stability (847.0 mAh g-1 after 1000 cycles at 2.0 A g-1). Upon pairing with LiNi0.6Co0.2Mn0.2O2 (NCM622), the assembled Si@TiSi2@NC||NCM622 pouch-type full cell exhibits exceptional cycling stability, retaining 90.1% of its capacity after 160 cycles at 0.5 C.

A Cu/MnOx Composite with Copper-Doping-Induced Oxygen Vacancies as a Cathode for Aqueous Zinc-Ion Batteries.

Aqueous zinc-ion batteries are anticipated to be the next generation of important energy storage devices to replace lithium-ion batteries due to the ongoing use of lithium resources and the safety hazards associated with organic electrolytes in lithium-ion batteries. Manganese-based compounds, including MnOx materials, have prominent places among the many zinc-ion battery cathode materials. Additionally, Cu doping can cause the creation of an oxygen vacancy, which increases the material's internal electric field and enhances cycle stability. MnOx also has great cyclic stability and promotes ion transport. At a current density of 0.2 A g-1, the Cu/MnOx nanocomposite obtained a high specific capacitance of 304.4 mAh g-1. In addition, Cu/MnOx nanocomposites showed A high specific capacity of 198.9 mAh g-1 after 1000 cycles at a current density of 0.5 A g-1. Therefore, Cu/MnOx nanocomposites are expected to be a strong contender for the next generation of zinc-ion battery cathode materials in high energy density storage systems.

Dead Lithium in Lithium Metal Batteries: Formation, Characterization and Strategies.

Lithium (Li) metal anode (LMA) replacing graphite anode for developing Li metal batteries (LMB) with the higher energy density has attracted much attention. However, LMA faces many issues, e. g., Li dendrites, dead Li and the side reactions, which causes the safety hazards and low coulomb efficiency (CE) of battery, therefore, LMB still cannot replace the current Li ion battery for practical use. Among those issues, dead Li is one of the decisive factors affecting the CE of LMB. To better understand dead Li, we summarize the recent work about the generation of dead Li, its impact on batteries performance, and the strategies to reuse and eliminate dead Li. Finally, the prospect of the future LMA and resultant LMB is also put forward.

Imidazole-Intercalated Cobalt Hydroxide Enabling the Li+ Desolvation/Diffusion Reaction and Flame Retardant Catalytic Dynamics for Lithium Ion Batteries.

Lithium-ion batteries have found extensive applications due to their high energy density and low self-discharge rates, spanning from compact consumer electronics to large-scale energy storage facilities. Despite their widespread use, challenges such as inherent capacity degradation and the potential for thermal runaway hinder sustainable development. In this study, we introduce a unique approach to synthesize anode materials for lithium-ion batteries, specifically imidazole-intercalated cobalt hydroxide. This innovative material significantly enhances the Li+ desolvation/diffusion reaction and flame-retardant dynamics through complexing and catalytic synergetic effects. The lithium-ion batteries incorporating these materials demonstrate exceptional performance, boasting an impressive capacity retention of 997.91 mAh g-1 after 500 cycles. This achievement can be attributed to the optimization of the solid electrolyte interphase (SEI) interface engineering, effectively mitigating anode degradation and minimizing electrolyte consumption. Experimental and theoretical calculations validate these improvements. Importantly, imidazole intercalated Co(OH)2 (MI-Co(OH)2) exhibits a remarkable catalytic effect on electrolyte carbonization and the conversion of CO to CO2. This dual action suppresses smoke and reduces toxicity significantly. The presented work introduces a novel approach to realizing high-performance and safe lithium-ion batteries, addressing key challenges in the pursuit of sustainable energy solutions.

Achieving high-capacity and durable sodium storage by constructing a binder-free nanotube array architecture of iron phosphide/carbon.

The conversion-type anode material of iron phosphide (FeP) promises enormous prospects for Na-ion battery technology due to its high theoretical capacity and cost-effectiveness. However, the poor reaction kinetics and large volume expansion of FeP significantly degrade the sodium storage, which remains a daunting challenge. Herein, we demonstrate a binder-free nanotube array architecture constructed by FeP@C hybrid on carbon cloth as advanced anodes to achieve fast and stable sodium storage. The nanotubular structure functions in multiple roles of providing short electron/ion transport distances, smooth electrolyte diffusion channels, and abundant active sites. The carbon layer could not only pave high-speed pathways for electron conductance but also cushion the volume change of FeP. Benefiting from these structural virtues, the FeP@C anode receives a high reversible capacity of 881.7 mAh/g at 0.1 A/g, along with a high initial Coulombic efficiency of 90% and excellent rate capability and cyclability in half and full cells. Moreover, the sodium energy reaction kinetics and mechanism of FeP@C are systematically studied. The present work offers a rational design and construction of high-capacity anode materials for high-energy-density Na-ion batteries.

High-capacity data hiding for medical images based on the mask-RCNN model.

This study introduces a novel approach for integrating sensitive patient information within medical images with minimal impact on their diagnostic quality. Utilizing the mask region-based convolutional neural network for identifying regions of minimal medical significance, the method embeds information using discrete cosine transform-based steganography. The focus is on embedding within "insignificant areas", determined by deep learning models, to ensure image quality and confidentiality are maintained. The methodology comprises three main steps: neural network training for area identification, an embedding process for data concealment, and an extraction process for retrieving embedded information. Experimental evaluations on the CHAOS dataset demonstrate the method's effectiveness, with the model achieving an average intersection over union score of 0.9146, indicating accurate segmentation. Imperceptibility metrics, including peak signal-to-noise ratio, were employed to assess the quality of stego images, with results showing high capacity embedding with minimal distortion. Furthermore, the embedding capacity and payload analysis reveal the method's high capacity for data concealment. The proposed method outperforms existing techniques by offering superior image quality, as evidenced by higher peak signal-to-noise ratio values, and efficient concealment capacity, making it a promising solution for secure medical image handling.

Statistical analysis of VEXLPE wear against alumina produced by a new 200-station, multidirectional pin-on-disk device.

With low wear rates shown by contemporary bearing materials of total hip prostheses, the standard deviation of wear rate is relatively high. Therefore, large sample sizes are needed for an adequate power of test. Because wear tests take a long time, it is practical to test several samples simultaneously. A new high-capacity, multidirectional wear test device, called the SuperCTPOD-200, was introduced. A 3 million-cycle wear test with an unprecedented sample size of 200 was performed for VEXLPE. The duration of the test was 6 weeks. The wear factor was normally distributed with a mean ± SD of 1.64 × 10-7 mm3/Nm ± 0.22 × 10-7 mm3/Nm (n = 200). The observation that SD was 13.1% of the mean can be useful in power analyses of future tests with other highly cross-linked polyethylenes. Burnishing was the most typical feature on the worn pins, which was in agreement with clinical findings on retrieved acetabular liners. The present study emphasizes statistics that often plays a minor role only in wear studies.