Strong yet flexible ceramic aerogel.

Ceramic aerogels are highly efficient, lightweight, and chemically stable thermal insulation materials but their application is hindered by their brittleness and low strength. Flexible nanostructure-assembled compressible aerogels have been developed to overcome the brittleness but they still show low strength, leading to insufficient load-bearing capacity. Here we designed and fabricated a laminated SiC-SiOx nanowire aerogel that exhibits reversible compressibility, recoverable buckling deformation, ductile tensile deformation, and simultaneous high strength of up to an order of magnitude larger than other ceramic aerogels. The aerogel also shows good thermal stability ranging from -196 °C in liquid nitrogen to above 1200 °C in butane blow torch, and good thermal insulation performance with a thermal conductivity of 39.3 ± 0.4 mW m-1 K-1. These integrated properties make the aerogel a promising candidate for mechanically robust and highly efficient flexible thermal insulation materials.

Anti-Shedding Nickel-Protection-Layer Boosting an Ultrahigh Loading Carbon Fiber@Co-NiSx Electrode to Deliver Superior Areal/Volumetric/Gravimetric Capacitance.

Challenges remain to show good capacitive performance while achieving high loadings of active materials for supercapacitors. Trying to realize this version, a nickel-protecting carbon fiber paper@Co-doped NiSx (Ni-CP@Co-NiSx) electrode with high specific gravimetric, areal, and volumetric capacitance is reported in this work. This free-standing electrode is prepared by an electroplating-hydrothermal-electroplating (EHE) three-step method to achieve a high loading of almost 26.7 mg cm-2. The cobalt-doping and nickel-protection strategies effectively decrease the impedance and inhibit the active material dropping from the electrode resulting from the expansion stress, which endows the Ni-CP@Co-NiSx electrode with a high rate and good cycling performance, especially with an ultrahigh specific areal/volumetric/gravimetric capacitance of 53.3 F cm-2/2807 F cm-3/1997 F g-1 at 5 mA cm-2, respectively. Employing activated carbon functionalized with riboflavin (AC/VB2) as a negative electrode, the asymmetric supercapacitor device delivers a very high energy density of up to 60.4 W h kg-1. This work demonstrates that electrodes with a high loading density and excellent performance can be obtained by the combination of the EHE method to adjust the internal conductivity and external structural stability.

Synergizing Hydrogen Spillover and Deprotonation by the Internal Polarization Field in a MoS2 /NiPS3 Vertical Heterostructure for Boosted Water Electrolysis.

Hydrogen spillover (HSo) has emerged to upgrade the hydrogen evolution reaction (HER) activity of Pt-support electrocatalysts, but it is not applicable to the deprotonated oxygen evolution reaction (OER). Non-precious catalysts that can perform well in both HSo and deprotonation (DeP) are extremely desirable for a sustainable hydrogen economy. Herein, an affordable MoS2 /NiPS3 vertical heterostructure catalyst is presented to synergize HSo and DeP for efficient water electrolysis. The internal polarization field (IPF) is clarified as the driving force of HSo in HER electrocatalysis. The HSo from the MoS2 edge to NiPS3 can activate the NiPS3 basal plane to boost the HER activity of the MoS2 /NiPS3 heterostructure (112 mV vs reversible hydrogen electrode (RHE) at 10 mA cm-2 ), while for OER, the IPF in the heterostructure can facilitate the hydroxyl diffusion and render MoS2 -to-NiPS3 /P-to-S dual-pathways for DeP. As a result, the stacking of OER-inactive MoS2 on the NiPS3 surface still brings intriguing OER enhancements. With them serving as electrode couples, the overall water splitting is attested stably with a cell voltage of 1.64 V at 10 mA cm-2 . This research puts forward the IPF as the criterion in the rational design of HSo/DeP-unified non-precious catalysts for efficient water electrolysis.

Highly Stretchable, Crack-Insensitive and Compressible Ceramic Aerogel.

Ceramic aerogels are attractive candidates for high-temperature thermal insulation, catalysis support, and ultrafiltration materials, but their practical applications are usually limited by brittleness. Recently, reversible compressibility has been realized in flexible nanostructures-based ceramic aerogels. However, these modified aerogels still show fast and brittle fracture under tension. Herein, we demonstrate achieving reversible stretch and crack insensitivity in a highly compressible ceramic aerogel through engineering its microstructure by using curly SiC-SiOx bicrystal nanowire as the building blocks. The aerogel exhibits large-strain reversible stretch (20%) and good resistance to high-speed tensile fatigue test. Even for a prenotched sample, a reversible stretch at 10% strain is achieved, indicating good crack resistance. The aerogel also displays reversible compressibility up to 80% strain, ultralow thermal conductivity of 28.4 mW m-1 K-1, and excellent thermal stability even at temperatures as high as 1200 °C in butane blow torch or as low as -196 °C in liquid nitrogen. Our findings show that the attractive tensile properties arise from the deformation, interaction, and reorientation of the curly nanowires which could reduce stress concentration and suppress crack initiation and growth during tension. This study not only expands the applicability of ceramic aerogels to conditions involving complex dynamic stress under extreme temperature conditions but also benefits the design of other highly stretchable and crack-resistant porous ceramic materials for various applications.

A calcium fluoride composite reduction graphene oxide functional separator for lithium-sulfur batteries to inhibit polysulfide shuttling and mitigate lithium dendrites.

Lithium-sulfur (Li-S) batteries have attracted tremendous attention as promising next-generation energy-storage systems due to their high specific capacity and high specific energy. However, the shuttle of polysulfides and the growth of Li dendrites severely obstruct the practical applications of these batteries. In this work, a functional separator is designed and fabricated in which nano-calcium fluoride (CaF2) particles are embedded in reduced graphene oxide (rGO) and bladed on a PP separator. The density functional theory (DFT) calculations of the adsorption energy and bond length reveal that CaF2 has a satisfying adsorption and catalytic effect on polysulfides (Li2Sn). The factional separator could accelerate homogenous Li+ flow and retard the growth of Li dendrites. In addition, an initial specific capacity of 1504 mAh g-1 at 0.05C is achieved, and it still retains a discharge capacity of 1050 mAh g-1 over 100 cycles at 0.2C. Moreover, the capacity decay rate is only 0.06% per cycle over 420 cycles at a high current density of 0.5 C. The excellent performance could be attributed to the CaF2@rGO modified separator not only accelerating the transmission of electrons but also effectively inhibiting the shuttling of polysulfides. This work provides a better method for attaining practical applications of high-performance lithium-sulfur batteries.

Electrospinning Highly Dispersed Ru Nanoparticle-Embedded Carbon Nanofibers Boost CO2 Reduction in a H2/CO2 Fuel Cell.

A H2/CO2 fuel cell is a promising device that can convert CO2 into hydrocarbon fuel with electricity generation. Herein, a facile electrospinning method has been used to synthesize the embedded Ru-CNF catalyst in which Ru nanoparticles are dispersed homogeneously within N-doped carbon nanofibers. This catalyst exhibits a high CH4 production rate of 308.46 µmol gcat-1 h-1 at 170 °C, which is superior to that of the Ru/CNF (242.53 µmol gcat-1 h-1) and Ru/CNT (194.24 µmol gcat-1 h-1). The enhanced CO2RR performance of Ru-CNF is ascribed to the well-distributed Ru nanoparticles within the CNF matrix and synergistic effect of Ru sites with N species, which results in forming the increased CO2RR active sites, hence improving the catalytic activity. Simultaneously, it can achieve a peak power density of 1.8 W m-2 on the strength of anodic (H2 oxidation) and cathodic (CO2 reduction and H2 evolution) reactions with remarkable stability. Such findings give a theoretical basis of CO2RR in the H2/CO2 fuel cell system, which could hold great value to further develop the high-efficiency catalysts for CO2 reduction.

Potassium Nickel Iron Hexacyanoferrate as Ultra-Long-Life Cathode Material for Potassium-Ion Batteries with High Energy Density.

The abundant reserve and low price of potassium resources promote K-ion batteries (KIBs) becoming a promising alternative to Li-ion batteries, while the large ionic radius of K-ions creates a formidable challenge for developing suitable electrodes. Here Ni-substituted Prussian blue analogues (PBAs) are investigated comprehensively as cathodes for KIBs. The synthesized K1.90Ni0.5Fe0.5[Fe(CN)6]0.89·0.42H2O (KNFHCF-1/2) takes advantage of the merits of high capacity from electrochemically active Fe-ions, outstanding electrochemical kinetics induced by decreased band gap and K-ion diffusion activation energy, and admirable structure stability from inert Ni-ions. Therefore, a high first capacity of 81.6 mAh·g-1 at 10 mA·g-1, an excellent rate property (53.4 mAh·g-1 at 500 mA·g-1), and a long-term lifespan over 1000 cycles with the lowest fading rate of 0.0177% per cycle at 100 mA·g-1 can be achieved for KNFHCF-1/2. The K-ion intercalation/deintercalation proceeds through a facile solid solution mechanism, allowing 1.5-electron transfer based on low- and high-spins FeII/FeIII couples, which is verified by ex situ XRD, XPS, and DFT calculations. The K-ion full battery is also demonstrated using a graphite anode with a high energy density of 282.7 Wh·kg-1. This work may promote more studies on PBA electrodes and accelerate the development of KIBs.

Improving electrochemical performances of Lithium-rich oxide by cooperatively doping Cr and coating Li3PO4 as cathode material for Lithium-ion batteries.

Lithium-rich layered oxides exhibit one of the highest reversible discharge capacities among cathode materials for lithium-ion batteries. However, their voltage decay and poor cycle stability severely restrict their use as a commercial cathode material. In this work, a novel approach of that combines Cr doping and a Li3PO4 coating was designed to address the problems associated with lithium-rich Li1.2Mn0.54Ni0.13Co0.13O2 materials. The synergistic method not only increases the discharge capacity and cycle stability but also decreases the voltage decay. The 1.0 wt% Li3PO4 coating and 0.08 Cr doping on Li1.2Mn0.54Ni0.13Co0.13O2 cathode shows a capacity retention of 76.5% compared to the 59.0% capacity retention for the pristine electrode after 200 cycles. The initial discharge capacity is also increased from 255.8 mAh·g-1 to 265.2 mAh·g-1. In addition, the discharge voltage decay decreases from 0.84 V to 0.39 V after 200 cycles as a result of the Cr doping and Li3PO4 coating. These enhanced electrochemical properties are attributed to the fact that the Cr doping stabilized the layered structure and inhibited its phase transformation to the spinel phase, and the Li3PO4 coating confined the interfacial side reactions between the electrode and electrolyte. This work may provide a new method to solve the subsistent problems of lithium-rich cathode materials.

Nonstoichiometry of Li-rich cathode material with improved cycling ability for lithium-ion batteries.

Lithium-rich layered oxides are considered as promising cathode materials for lithium-ion batteries due to its high capacity, but the rapid decay of capacity and operating voltage are great challenges to achieve its commercial application. In this work, the nonstoichiometry of Li-rich layered oxide Li1.2Mn0.6Ni0.2O2 was designed by directly declining the Mn amounts in the form of Li1.2MnxNi0.2O2 (x = 0.59, 0.57, 0.55). The nonstoichiometric sample Li1.2Mn0.55Ni0.2O2 exhibits a capacity of 170.73 mAh g-1 at 0.5 C, a little lower than 187.29 mAh g-1 of Li1.2Mn0.6Ni0.2O2, however, better cycling stability of operating voltage and capacity is attained with the reduction of Mn amounts, compared to that of Li1.2Mn0.6Ni0.2O2. The capacity retention of Li1.2Mn0.55Ni0.2O2 is enhanced to 88.7% via 74.7% of Li1.2Mn0.6Ni0.2O2 after 100 cycles at 0.5 C. The declining value of operating voltage for Li1.2Mn0.55Ni0.2O2 is 0.200 V as compared to 0.559 V for Li1.2Mn0.6Ni0.2O2. X-ray photoelectron spectra (XPS) was employed to confirm the existence of Ni3+ in the nonstoichiometric samples, and the amounts of Ni3+ increase along the Mn contents decrease. The improvement of electrochemical properties for nonstoichiometric samples is attributed to the presence of Ni3+ due to Ni3+ can defer the transition of layered-to-spinel structure through decreasing the Li/Ni mixing.

Ultralight, Recoverable, and High-Temperature-Resistant SiC Nanowire Aerogel.

Ultralight ceramic aerogels with the property combination of recoverable compressibility and excellent high-temperature stability are attractive for use in harsh environments. However, conventional ceramic aerogels are usually constructed by oxide ceramic nanoparticles, and their practical applications have always been limited by the brittle nature of ceramics and volume shrinkage at high temperature. Silicon carbide (SiC) nanowire offers the integrated properties of elasticity and flexibility of one-dimensional (1D) nanomaterials and superior high-temperature thermal and chemical stability of SiC ceramics, which makes it a promising building block for compressible ceramic nanowire aerogels (NWAs). Here, we report the fabrication and properties of a highly porous three-dimensional (3D) SiC NWA assembled by a large number of interweaving 3C-SiC nanowires of 20-50 nm diameter and tens to hundreds of micrometers in length. The SiC NWA possesses ultralow density (∼5 mg cm-3), excellent mechanical properties of large recoverable compression strain (>70%) and fatigue resistance, refractory property, oxidation and high-temperature resistance, and thermal insulating property (0.026 W m-1 K-1 at room temperature in N2). When used as absorbents, the SiC NWAs exhibit an adsorption selectivity of low-viscosity organic solvents with high absorption capacity (130-237 g g-1). The successful fabrication of such an attractive material may provide promising perspectives to the design and fabrication of other compressible and multifunctional ceramic NWAs.

High electrochemical performance of nanocrystallized carbon-coated LiFePO4 modified by tris(pentafluorophenyl) borane as a cathode material for lithium-ion batteries.

Tris(pentafluorophenyl) borane (C18BF15) was first adopted as a boron source, which clearly demonstrated its modification effects. XPS and EDX mapping proved that boron can be successfully doped into a carbon layer. The high number of defects in the carbon induced by boron was demonstrated via Raman spectroscopy and thus, the electric conductivity of LiFePO4 was greatly enhanced. The boron-doped composite possessed a higher specific discharge capacity and rate capability than the undoped sample. For instance, the reversible specific capacity for the boron-doped cathode reached 165.8 mA h g-1 at 0.5C, which was almost close to its theoretical capacity (166 mA h g-1). Even at a high rate of 5C, it still possessed a high specific capacity of 124.8 mA h g-1. This provides for the possibility that boron-doped carbon-coated LiFePO4 cathodes may deliver high energy and power density for rechargeable lithium-ion batteries.

Quasi-zero-dimensional cobalt-doped CeO2 dots on Pd catalysts for alcohol electro-oxidation with enhanced poisoning-tolerance.

Deactivation of an anode catalyst resulting from the poisoning of COad-like intermediates is one of the major problems for methanol and ethanol electro-oxidation reactions (MOR & EOR), and remains a grand challenge towards achieving high performance for direct alcohol fuel cells (DAFCs). Herein, we report a new approach for the preparation of ultrafine cobalt-doped CeO2 dots (Co-CeO2, d = 3.6 nm), which can be an effective anti-poisoning promoter for Pd catalysts towards MOR and EOR in alkaline media. Compared to Pd/CeO2 and pure Pd, the hybrid Pd/Co-CeO2 nanocomposite catalyst exhibited a much enhanced activity and remarkable anti-poisoning ability for both MOR and EOR. The nanocomposite catalyst showed much higher mass activity (4×) than a state-of-the-art PtRu catalyst. The promotional mechanism was elucidated using extensive characterization and density-functional theory (DFT). A bifunctional effect of the Co-CeO2 dots was discovered to be due to (i) an enhanced electronic interaction between Co-CeO2 and Pd dots and (ii) the increased oxygen storage capacity of Co-CeO2 dots to facilitate the oxidation of COad. Therefore, the Pd/Co-CeO2 nanocomposite appears to be a promising catalyst for advanced DAFCs with low cost and high performance.

Super-strong dislocation-structured high-carbon martensite steel.

High-carbon martensite steels (with C > 0.5 wt.%) are very hard but at the same time as brittle as glass in as-quenched or low-temperature-tempered state. Such extreme brittleness, originating from a twin microstructure, has rendered these steels almost useless in martensite state. Therefore, for more than a century it has been a common knowledge that high-carbon martensitic steels are intrinsically brittle and thus are not expected to find any application in harsh loading conditions. Here we report that these brittle steels can be transformed into super-strong ones exhibiting a combination of ultrahigh strength and significant toughness, through a simple grain-refinement treatment, which refines the grain size to ~4 µm. As a result, an ultra-high tensile strength of 2.4~2.6 GPa, a significant elongation of 4~10% and a good fracture toughness (K1C) of 23.5~29.6 MPa m1/2 were obtained in high-carbon martensitic steels with 0.61-0.65 wt.% C. These properties are comparable with those of "the king of super-high-strength steels"-maraging steels, but achieved at merely 1/30~1/50 of the price. The drastic enhancement in mechanical properties is found to arise from a transition from the conventional twin microstructure to a dislocation one by grain refinement. Our finding may provide a new route to manufacturing super-strong steels in a simple and economic way.

Effect of Defects on Decay of Voltage and Capacity for Li[Li0.15Ni0.2Mn0.6]O2 Cathode Material.

Lithium-rich manganese metal layered oxides are very promising cathode materials for high-energy-density lithium-ion batteries, but improvement in voltage decay and capacity fade is a great challenge, which is mainly related to the structural instability or reconstruction of material's surface. Defects, such as part lattice distortions, local cation disordering and atomic ununiformity, often aggravate the further structural changes upon cycling. In this paper, we found that PEG contributed to form better layered structure, well crystallinity, uniform composition and polyhedral nanoparticles for Li[Li0.15Ni0.2Mn0.6]O2 (LNMO). On the basis of the comparative trial, a mechanism of electronegativity difference is proposed to elucidate cation nonuniform distribution. Higher electronegativity of Ni (1.91) than Mn (1.55) show a stronger ability of attraction between Ni and O atoms, and then led to Ni atoms show stronger diffusion driving force toward particle surface to contact the rich O atoms during sintering in air. However, PEG polymer can form a better barrier for more O atoms to attract Ni and Mn atoms on particle surface so that facilitated a uniform distribution. The electrochemical test indicated that the decay of discharge capacity and working voltage was mitigated, which was identified by the result of HRTEM analysis that the initial less defect structure obviously retarded the phase transformation from the layered to spinel after 50 cycles. Therefore, defects are crucial for understanding the voltage fade and capacity decay, and the improvement of performance also demonstrates that designing optimum compositions and ordering atomic arrangements will contribute to stabilize the surface structure and restrain inherent phase transitions.

Rational Design of NiCoO2@SnO2 Heterostructure Attached on Amorphous Carbon Nanotubes with Improved Lithium Storage Properties.

It still remains very challenging to design proper heterostructures to enhance the electrochemical performance of transition metal oxide-based anode materials for lithium-ion batteries. Here, we synthesized the NiCoO2 nanosheets@SnO2 layer heterostructure supported by amorphous carbon nanotubes (ACNTs) which is derived from polymeric nanotubes (PNTs) by a stepwise method. The inner SnO2 layer not only provides a considerable capacity contribution but also produces the extra Li2O to promote the charge process of NiCoO2 and thus results in a rising cycling performance. Combining with the contribution of ACNTs backbone and ultrathin NiCoO2 nanosheets, the specific capacities of these one-dimensional nanostructures show an interesting gradually increasing trend even after 100 cycles at 400 mA g(-1) with a final result of 1166 mAh g(-1). This approach can be an efficient general strategy for the preparation of mixed-metal-oxide one-dimensional nanostructures and this innovative design of hybrid electrode materials provides a promising approach for batteries with improved electrochemical performance.

Direct evidence for local symmetry breaking during a strain glass transition.

Strain glass transition is a unique nanoscale displacive transition with local symmetry breaking while maintaining the macroscopic symmetry or average structure unchanged. It usually occurs in the "nonmartensitic" composition range of a martensitic system. So far, only indirect evidence exists for such a transition, essentially from macroscopic measurements and low-resolution transmission electron microscopy observations, and there is a lack of direct evidence for the speculated local symmetry breaking and the sluggish nature of the glass transition. In this Letter we report in situ high-resolution transmission electron microscopy observations on a Ti50(Pd41Cr9) strain glass alloy and direct evidence for these key issues. Our results show that at temperatures well above the strain glass transition temperature (Tg), the lattice is essentially an undistorted B2 structure. With approaching Tg, the local symmetry breaking gradually occurs with the formation and growth of nanomartensite clusters with a combined stacking period of three and four plane intervals, but the average structure measured by x-ray diffraction remains B2. These nanomartensite clusters become finally frozen below Tg. Our results provide not only a microscopic basis for the macroscopic properties of strain glass, but also new insights into a range of possible applications of this unique class of materials.

catena-Poly[[[diaqua-diformato-cobalt(II)]-µ-1,4-bis-(1H-benzimidazol-1-yl)benzene] dihydrate].

In the title coordination polymer, {[Co(CHO(2))(2)(C(20)H(14)N(4))(H(2)O)(2)]·2H(2)O}(n), the Co(II) atom (site symmetry [Formula: see text]) is coordinated by two formate O atoms, two water O atoms and two N atoms from two 1,4-bis-(1H-benzimidazol-1-yl)benzene ligands (L), resulting in a distorted trans-CoN(2)O(4) octa-hedral coordin-ation environment. The complete L ligand is generated by crystallographic inversion symmetry and serves to bridge the cobalt ions into a chain propagating in [1[Formula: see text][Formula: see text]]. The dihedral angle between the central benzene ring and the imidazole ring system is 38.48 (12)°. O-H⋯O hydrogen bonds involving both the coordinated and uncoordinated water mol-ecules occur and help to link the chains together.