Ni/Graphene Coating for Enhanced Corrosion Resistance of Metal Foam Flow Field in Simulated PEMFC Cathode Environment.

Metal foam flow field suffers serious corrosion issues in proton exchange membrane fuel cells due to its large surface area. Ni and Ni/graphene coatings are prepared under constant and gradient current modes, respectively, to improve the corrosion resistance. The effect of the electrodeposition current mode and the deposition mechanism is studied. Compared with Ni coating, Ni/graphene coating brings low corrosion current density and high coating resistance, effectively enhancing the stability of Ni foam in an acidic environment. Different from Ni coating with a single layer, Ni/graphene deposits have core-shell structure, with graphene coated on the surface of Ni nanoparticles. It is shown that graphene deposits cover the Ni particles during the electrodeposition, which protects nickel particles from agglomeration and forms an inert film on the surface of the porous structure. After an 8 h constant potential test, no significant pitting is observed on the surface of Ni/graphene coating, showing excellent anticorrosion performance. As to the effect of the deposition current mode, it is shown that more composite particles deposit on the upper layer under the gradient current mode, which brings denser protective film and fewer surface defects on the surface. Ni/graphene coating electrodeposited under a gradient current mode between 0 and 10 mA·cm-2 exhibits the lowest corrosion current densities. The values at 50 and 80 °C are only 62.9 and 26.0% of those of uncoated Ni foam, respectively.

Production of high-energy 6-Ah-level Li | |LiNi0.83Co0.11Mn0.06O2 multi-layer pouch cells via negative electrode protective layer coating strategy.

Stable lithium metal negative electrodes are desirable to produce high-energy batteries. However, when practical testing conditions are applied, lithium metal is unstable during battery cycling. Here, we propose poly(2-hydroxyethyl acrylate-co-sodium benzenesulfonate) (PHS) as negative electrode protective layer. The PHS contains soft poly (2-hydroxyethyl acrylate) and poly(sodium p-styrene sulfonate), which improve electrode flexibility, connection with the Cu current collector and transport of Li ions. Transmission electron cryomicroscopy measurements reveal that PHS induces the formation of a solid electrolyte interphase with a fluorinated rigid and crystalline internal structure. Furthermore, theoretical calculations suggest that the -SO3- group of poly(sodium p-styrene sulfonate) promotes Li-ion motion towards interchain migration through cation-dipole interaction, thus, enabling uniform Li-ion diffusion. Electrochemical measurements of Li | |PHS-coated-Cu coin cells demonstrate an average Coulombic efficiency of 99.46% at 1 mA/cm2, 6 mAh/cm2 and 25 °C. Moreover, when the PHS-coated Li metal negative electrode is paired with a high-areal-capacity LiNi0.83Co0.11Mn0.06O2-based positive electrode in multi-layer pouch cell configuration, the battery delivers an initial capacity of 6.86 Ah (corresponding to a specific energy of 489.7 Wh/kg) and, a 91.1% discharge capacity retention after 150 cycles at 2.5 mA/cm2, 25 °C and 172 kPa.

Water Management Capacity of Metal Foam Flow Field for PEMFC under Flooding Situation.

Porous metal foam with complex opening geometry has been used as a flow field to enhance the distribution of reactant gas and the removal of water in polymer electrolyte membrane fuel cells. In this study, the water management capacity of a metal foam flow field is experimentally investigated by polarization curve tests and electrochemical impedance spectroscopy measurements. Additionally, the dynamic behavior of water at the cathode and anode under various flooding situations is examined. It is found that obvious flooding phenomena are observed after water addition both into the anode and cathode, which are alleviated during a constant-potential test at 0.6 V. Greater abilities of anti-flooding and mass transfer and higher current densities are found as the same amount of water is added at the anode. No diffusion loop is depicted in the impedance plots although a 58.3% flow volume is occupied by water. The maximum current density of 1.0 A cm-2 and the lowest Rct around 17 mΩ cm2 are obtained at the optimum state after 40 and 50 min of operation as 2.0 and 2.5 g of water are added, respectively. The porous metal pores store a certain amount of water to humidify the membrane and achieve an internal "self-humidification" function.

Surfactant Additives Containing Hydrophobic Fluorocarbon Chains and Hydrophilic Sulfonate Anion for Highly Reversible Zn Anode.

Aqueous zinc-ion batteries (AZIBs) show enormous potential as a large-scale energy storage technique. However, the growth of Zn dendrites and serious side reactions occurring at the Zn anode hinder the practical application of AZIBs. For the first time, we reported a fluorine-containing surfactant, i.e., potassium perfluoro-1-butanesulfonate (PPFBS), as an additive to the 2 M ZnSO4 electrolyte. Benefitting from its hydrophilic sulfonate anion and hydrophobic long fluorocarbon chain, PPFBS can promote the uniform distribution of Zn2+ flux at the anode/electrolyte interface, allowing the Zn/Zn cell to cycle for 2200 h. Furthermore, PPFBS could inhibit side reactions due to the existence of the perfluorobutyl sulfonate (C4F9SO3-) adsorption layer and the presence of C4F9SO3- in the solvation structure of Zn2+. The former can reduce the amount of H2O molecules and SO42- in contact with the Zn anode and C4F9SO3- entering the Zn2+-solvation structure by replacing SO42-. The Zn/Cu cell exhibits a superior average CE of 99.47% over 500 cycles. When coupled with the V2O5 cathode, the full cell shows impressive cycle stability. This work provides a simple, effective, and economical solution to the common issues of the Zn anode.

Enhanced Ageing Performance of Sulfonic Acid-Grafted Pt/C Catalysts.

Chemical functionalization of carbon support for Pt catalysts is a promising way to enhance the performance of catalysts. In this study, Pt/C catalysts grafted with various amounts of phenylsulfonic acid groups were prepared under mild conditions. The influence of sulfonic acid groups on the physiochemical characteristics and electrochemical activities of the modified catalysts were studied using X-ray diffraction, X-ray photoelectron spectroscopy, a transmission electron microscope, and cyclic voltammetry (CV). The presence of the chemical groups enhanced the hydrogen adsorption onto/desorption off the Pt surface during the CV cycling. In contrast, the hydrogen peaks of the grafted catalysts increased after 500 CV cycles, especially for Pt (111) facets. The highest electrochemical surface area (ECSA) after the aging test was obtained for the catalyst with 18.0 wt.% graft, which was ca. 87.3% higher than that of the non-functionalized Pt catalyst. In the density functional theory (DFT) calculation, it was proven that SO3H adsorption on the crystalline was beneficial for Pt stability. The adsorption energy and bond distance of the adsorbed SO3H on Pt (110), (100), and (111) surfaces were calculated. All the stable configurations were obtained when O from S-O single bond or S was bound to the Pt surface, with the adsorption energy following the trend of (111)F > (100)H > (110)H. This result was consistent with the ECSA experiment, which explained the high electrochemical stability of the sulfonic acid groups-grafted Pt/C catalyst.

High plasma levels of trimethylamine N-oxide are associated with poor outcome in intracerebral hemorrhage patients.

BACKGROUND AND AIMS: As a gut microbiota-dependent metabolite, trimethylamine N-oxide (TMAO) has been implicated in cardiovascular diseases. We aimed to investigate the relationship between the clinical outcomes and plasma TMAO concentrations in patients with acute intracerebral hemorrhage. METHODS: From January 2019 to October 2019, we prospectively enrolled intracerebral hemorrhage patients diagnosed within 6 h of symptoms onset. Plasma TMAO levels was measured for all patients within 24 h after admission. The primary outcome was functional outcome at 3 months. Patients were dichotomized as good (modified Rankin scale 0-3) and poor (modified Rankin scale 4-6). Secondary outcome included early neurological deterioration (END) and hematoma enlargement (HE). RESULTS: There were 307 patients (57.7% male) with a mean age of 66.8 years included in the study. The median TMAO levels was 3.2 µmol/L. END, HE, and 3-month poor outcome were detected in 59 (19.2%), 54 (17.6%), and 139 (45.3%) patients, respectively. After adjusting for potential confounders, the odds ratio for the highest quartile of TMAO compared with the lowest quartile was 3.65 (95% confidence interval, 1.43-9.30) for 3-month poor outcome. Furthermore, multiple-adjusted spline regression model showed a linear association between TMAO levels and poor outcome at 3 months (P = 0.013 for linearity). Similar significant findings were observed when functional outcome was analyzed by continuous mRS score. No association was found between TMAO levels and END and HE. CONCLUSIONS: The present study demonstrated that increased TMAO levels were independently correlated with 3-month function outcome after intracerebral hemorrhage.

Mass-Producible, Quasi-Zero-Strain, Lattice-Water-Rich Inorganic Open-Frameworks for Ultrafast-Charging and Long-Cycling Zinc-Ion Batteries.

Low-cost and high-safety aqueous Zn-ion batteries are an exceptionally compelling technology for grid-scale energy storage. However, their development has been plagued by the lack of stable cathode materials allowing fast Zn2+ -ion insertion and scalable synthesis. Here, a lattice-water-rich, inorganic-open-framework (IOF) phosphovanadate cathode, which is mass-producible and delivers high capacity (228 mAh g-1 ) and energy density (193.8 Wh kg-1 or 513 Wh L-1 ), is reported. The abundant lattice waters functioning as a "charge shield" enable a low Zn2+ -migration energy barrier, (0.66 eV) even close to that of Li+ within LiFePO4 . This fast intrinsic ion-diffusion kinetics, together with nanostructure effect, allow the achievements of ultrafast charging (71% state of charge in 1.9 min) and an ultrahigh power density (7200 W kg-1 at 107 Wh kg-1 ). Equally important, the IOF exhibits a quasi-zero-strain feature (<1% lattice change upon (de)zincation), which ensures ultrahigh cycling durability (3000 cycles) and Coulombic efficiencies of 100%. The cell-level energy and power densities reach ≈90 Wh kg-1 and ≈3320 W kg-1 , far surpassing commercial lead-acid, Ni-Cd, and Ni-MH batteries. Lattice-water-rich IOFs may open up new opportunities for exploring stable and fast-charging Zn-ion batteries.

Circular RNA VMA21 ameliorates sepsis-associated acute kidney injury by regulating miR-9-3p/SMG1/inflammation axis and oxidative stress.

Accumulating evidence suggests that circular RNAs have the abilities to regulate gene expression during the progression of sepsis-associated acute kidney injury. Circular RNA VMA21 (circVMA21), a recent identified circular RNA, could reduce apoptosis to alleviate intervertebral disc degeneration in rats and protect WI-38 cells from lipopolysaccharide-induced injury. However, the role of circVMA21 in sepsis-associated acute kidney injury (sepsis-associated AKI) is unknown. In this study, we first demonstrated that circVMA21 alleviated sepsis-associated AKI by reducing apoptosis and inflammation in rats and HK-2 cells. Additionally, to explore the molecule mechanism underlying the amelioration, after the bioinformatics analysis, we confirmed that miR-9-3p directly bound to circVMA21 by luciferase and RNA immunoprecipitation assay, and the effector protein of miR-9-3p was SMG1. Furthermore, the oxidative stress caused by sepsis-associated AKI was down-regulated by circVMA21. In conclusion, circVMA21 plays an important role in the regulating sepsis-associated AKI via adjusting miR-9-39/SMG1/inflammation axis and oxidative stress.

Approaching the voltage and energy density limits of potassium-selenium battery chemistry in a concentrated ether-based electrolyte.

Potassium-selenium (K-Se) batteries offer fairly high theoretical voltage (∼1.88 V) and energy density (∼1275 W h kgSe -1). However, in practice, their operation voltage is so far limited to ∼1.4 V, resulting in insufficient energy utilization and mechanistic understanding. Here, it is demonstrated for the first time that K-Se batteries operating in concentrated ether-based electrolytes follow distinctive reaction pathways involving reversible stepwise conversion reactions from Se to K2Se x (x = 5, 3, 2, 1). The presence of redox intermediates K2Se5 at ∼2.3 V and K2Se3 at ∼2.1 V, in contrast with previous reports, enables record-high average discharge plateau voltage (1.85 V) and energy density (998 W h kgSe -1 or 502 W h kgK2Se -1), both approaching the theoretical limits and surpassing those of previously reported Na/K/Al-Se batteries. Moreover, experimental analysis and first-principles calculations reveal that the effective suppression of detrimental polyselenide dissolution/shuttling in concentrated electrolytes, together with high electron conductibility of Se/K2Se x , enables fast reaction kinetics, efficient utilization of Se, and long-term cyclability of up to 350 cycles, which are impracticable in either K-S counterparts or K-Se batteries with low/moderate-concentration electrolytes. This work may pave the way for mechanistic understanding and full energy utilization of K-Se battery chemistry.

Safe, Low-Cost, Fast-Kinetics and Low-Strain Inorganic-Open-Framework Anode for Potassium-Ion Batteries.

A key challenge for potassium-ion batteries is to explore low-cost electrode materials that allow fast and reversible insertion of large-ionic-size K+ . Here, we report an inorganic-open-framework anode (KTiOPO4 ), which achieves a reversible capacity of up to 102 mAh g-1 (307 mAh cm-3 ), flat voltage plateaus at a safe average potential of 0.82 V (vs. K/K+ ), a long lifespan of over 200 cycles, and K+ -transport kinetics ≈10 times faster than those of Na-superionic conductors. Combined experimental analysis and first-principles calculations reveal a charge storage mechanism involving biphasic and solid solution reactions and a cell volume change (9.5 %) even smaller than that for Li+ -insertion into graphite (≈10 %). KTiOPO4 exhibits quasi-3D lattice expansion on K+ intercalation, enabling the disintegration of small lattice strain and thus high structural stability. The inorganic open-frameworks may open a new avenue for exploring low-cost, stable and fast-kinetic battery chemistry.

Highly reversible potassium-ion intercalation in tungsten disulfide.

Rechargeable potassium-ion batteries (PIBs) show promise beyond Li-ion technology in large-scale electrical-energy storage due to the abundance and low cost of potassium resources. However, the intercalation of large-size K+ generally results in irreversible structural degradation and short lifespan to the hosts, representing a major obstacle. Here, we report a new electrochemical K+-intercalation host, tungsten disulfide (WS2), which can store 0.62 K+ per formula unit with a reversible capacity of 67 mA h g-1 and well-defined voltage plateaus at an intrinsically safe average operation potential of 0.72 V versus K/K+. In situ X-ray diffraction and ex situ electron microscopy revealed the underlying intercalation mechanism, a relatively small cell volume change (37.81%), and high reversibility of this new battery chemistry. Such characteristics impart WS2 with ultrahigh structural stability and a long lifespan, regardless of deep or fast charging. WS2 achieved record-high cyclability among chalcogenides up to 600 cycles with 89.2% capacity retention at 0.3C, and over 1000 cycles with 96.3% capacity retention and an extraordinary average Coulombic efficiency of 99.90% at 2.2C. This intercalation electrochemistry may open up new opportunities for the design of long-cycle-life and high-safety PIBs.

Concentrated electrolytes stabilize bismuth-potassium batteries.

Storing as many as three K-ions per atom, bismuth is a promising anode material for rechargeable potassium-ion batteries that may replace lithium-ion batteries for large-scale electrical energy storage. However, Bi suffers from poor electrochemical cyclability in conventional electrolytes. Here, we demonstrate that a 5 molar (M) ether-based electrolyte, versus the typical 1 M electrolyte, can effectively passivate the bismuth surface due to elevated reduction resistance. This protection allows a bismuth-carbon anode to simultaneously achieve high specific capacity, electrochemical cyclability and Coulombic efficiency, as well as small potential hysteresis and improved rate capability. We show that at a high electrolyte concentration, the bismuth anode demonstrates excellent cyclability over 600 cycles with 85% capacity retention and an average Coulombic efficiency of 99.35% at 200 mA g-1. This "concentrated electrolyte" approach provides unexpected new insights to guide the development of long-cycle-life and high-safety potassium-ion batteries.

Superacid-Surfactant Exchange: Enabling Nondestructive Dispersion of Full-Length Carbon Nanotubes in Water.

Attaining aqueous solutions of individual, long single-walled carbon nanotubes is a critical first step for harnessing the extraordinary properties of these materials. However, the widely used ultrasonication-ultracentrifugation approach and its variants inadvertently cut the nanotubes into short pieces. The process is also time-consuming and difficult to scale. Here we present an unexpectedly simple solution to this decade-old challenge by directly neutralizing a nanotube-chlorosulfonic acid solution in the presence of sodium deoxycholate. This straightforward superacid-surfactant exchange eliminates the need for both ultrasonication and ultracentrifugation altogether, allowing aqueous solutions of individual nanotubes to be prepared within minutes and preserving the full length of the nanotubes. We found that the average length of the processed nanotubes is more than 350% longer than sonicated controls, with a significant fraction approaching ∼9 µm, a length that is limited by only the raw material. The nondestructive nature is manifested by an extremely low density of defects, bright and homogeneous photoluminescence in the near-infrared, and ultrahigh electrical conductivity in transparent thin films (130 Ω/sq at 83% transmittance), which well exceeds that of indium tin oxide. Furthermore, we demonstrate that our method is fully compatible with established techniques for sorting nanotubes by their electronic structures and can also be readily applied to graphene. This surprisingly simple method thus enables nondestructive aqueous solution processing of high-quality carbon nanomaterials at large-scale and low-cost with the potential for a wide range of fundamental studies and applications, including, for example, transparent conductors, near-infrared imaging, and high-performance electronics.

Li3PO4 Matrix Enables a Long Cycle Life and High Energy Efficiency Bismuth-Based Battery.

Bismuth is a lithium-ion battery anode material that can operate at an equilibrium potential higher than graphite and provide a capacity twice as high as that of Li4Ti5O12, making it intrinsically free from lithium plating that may cause catastrophic battery failure. However, the potential of bismuth is hampered by its inferior cyclability (limited to tens of cycles). Here, we propose an "ion conductive solid-state matrix" approach to address this issue. By homogeneously confining bismuth nanoparticles in a solid-state γ-Li3PO4 matrix that is electrochemically formed in situ, the resulting composite anode exhibits a reversible capacity of 280 mA hours per gram (mA h/g) at a rate of 100 mA/g and a record cyclability among bismuth-based anodes up to 500 cycles with a capacity decay rate of merely 0.071% per cycle. We further show that full-cell batteries fabricated from this composite anode and commercial LiFePO4 cathode deliver a stable cell voltage of ∼2.5 V and remarkable energy efficiency up to 86.3%, on par with practical batteries (80-90%). This work paves a way for harnessing bismuth-based battery chemistry for the design of high capacity, safer lithium-ion batteries to meet demanding applications such as electric vehicles.

Dual-template ordered mesoporous carbon/Fe2O3 nanowires as lithium-ion battery anodes.

Ordered mesoporous carbons (OMCs) are ideal host materials that can provide the desirable electrical conductivity and ion accessibility for high-capacity oxide electrode materials in lithium-ion batteries (LIBs). To this end, however, it is imperative to establish the correlations among material morphology, pore structure and electrochemical performance. Here, we fabricate an ordered mesoporous carbon nanowire (OMCNW)/Fe2O3 composite utilizing a novel soft-hard dual-template approach. The structure and electrochemical performance of OMCNW/Fe2O3 were systematically compared with single-templated OMC/Fe2O3 and carbon nanowire/Fe2O3 composites. This dual-template strategy presents synergetic effects combining the advantages of both soft and hard single-template methods. The resulting OMCNW/Fe2O3 composite enables a high pore volume, high structural stability, enhanced electrical conductivity and Li(+) accessibility. These features collectively enable excellent electrochemical cyclability (1200 cycles) and a reversible Li(+) storage capacity as high as 819 mA h g(-1) at a current density of 0.5 A g(-1). Our findings highlight the synergistic benefits of the dual-template approach to heterogeneous composites for high performance electrochemical energy storage materials.

Blocking Oxidation Failures of Carbon Nanotubes through Selective Protection of Defects.

The selective growth of Al2 O3 islands over defect sites on the surface of carbon nanotubes significantly increases the oxidation breakdown threshold to 6.8 W cm(-2) , more than double than that of unprotected films. The elevated input power enables thermoacoustic emissions at loud audible sound pressure levels of 90.1 dB, which are inaccessible with the unprotected films.

Ammonium Laurate Surfactant for Cleaner Deposition of Carbon Nanotubes.

Experiments probing the properties of individual carbon nanotubes (CNTs) and those measuring bulk composites show vastly different results. One major issue limiting the results is that the procedures required to separate and test CNTs introduce contamination that changes the properties of the CNT. These contamination residues often come from the resist used in lithographic processing and the surfactant used to suspend and deposit the CNTs, commonly sodium dodecyl sulfate (SDS). Here we present ammonium laurate (AL), a surfactant that has previously not been used for this application, which differs from SDS only by substitution of ionic constituents but shows vastly cleaner depositions. In addition, we show that compared to SDS, AL-suspended CNTs have greater shelf stability and more selective dispersion. These results are verified using transmission electron microscopy, atomic force microscopy, ζ-potential measurements, and Raman and absorption optical spectroscopy. This surfactant is simple to prepare, and the nanotube solutions require minimal sonication and centrifugation in order to outperform SDS.

Selective breakdown of metallic pathways in double-walled carbon nanotube networks.

Covalently functionalized, semiconducting double-walled carbon nanotubes exhibit remarkable properties and can outperform their single-walled carbon nanotube counterparts. In order to harness their potential for electronic applications, metallic double-walled carbon nanotubes must be separated from the semiconductors. However, the inner wall is inaccessible to current separation techniques which rely on the surface properties. Here, the first approach to address this challenge through electrical breakdown of metallic double-walled carbon nanotubes, both inner and outer walls, within networks of mixed electronic types is described. The intact semiconductors demonstrate a ∼62% retention of the ON-state conductance in thin film transistors in response to covalent functionalization. The selective elimination of the metallic pathways improves the ON/OFF ratio, by more than 360 times, to as high as 40 700, while simultaneously retaining high ON-state conductance.

Interfacial oxygen stabilizes composite silicon anodes.

Silicon can store Li(+) at a capacity 10 times that of graphite anodes. However, to harness this remarkable potential for electrical energy storage, one has to address the multifaceted challenge of volume change inherent to high capacity electrode materials. Here, we show that, solely by chemical tailoring of Si-carbon interface with atomic oxygen, the cycle life of Si/carbon matrix-composite electrodes can be substantially improved, by 300%, even at high mass loadings. The interface tailored electrodes simultaneously attain high areal capacity (3.86 mAh/cm(2)), high specific capacity (922 mAh/g based on the mass of the entire electrode), and excellent cyclability (80% retention of capacity after 160 cycles), which are among the highest reported. Even at a high rate of 1C, the areal capacity approaches 1.61 mAh/cm(2) at the 500th cycle. This remarkable electrochemical performance is directly correlated with significantly improved structural and electrical interconnections throughout the entire electrode due to chemical tailoring of the Si-carbon interface with atomic oxygen. Our results demonstrate that interfacial bonding, a new dimension that has yet to be explored, can play an unexpectedly important role in addressing the multifaceted challenge of Si anodes.

Hoop-strong nanotubes for battery electrodes.

The engineering of hollow nanostructures is a promising approach to addressing instabilities in silicon-based electrodes for lithium-ion batteries. Previous studies showed that a SiOx coating on silicon nanotubes (SiNTs) could function as a constraining layer and enhance capacity retention in electrodes with low mass loading, but we show here that similarly produced electrodes having negligible SiOx coating and significantly higher mass loading show relatively low capacity retention, fading quickly within the early cycles. We find that the SiNT performance can still be enhanced, even in electrodes with high mass loading, by the use of Ni functional coatings on the outer surface, leading to greatly enhanced capacity retention in a manner that could scale better to industrially relevant battery capacities. In situ transmission electron microscopy studies reveal that the Ni coatings suppress the Si wall from expanding outward, instead carrying the large hoop stress and forcing the Si to expand inward toward the hollow inner core. Evidence shows that these controlled volume changes in Ni-coated SiNTs, accompanied by the electrochemically inert nature of Ni coatings, unlike SiOx, may enhance the stability of the electrolyte at the outer surface against forming a thick solid electrolyte interphase (SEI) layer. These results provide useful guidelines for designing nanostructured silicon electrodes for viable lithium-ion battery applications.