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At least 1,567 records · Page 87

Elucidating Cycling Rate-Dependent Electrochemical Strains in Sodium Iron Phosphate Cathodes for Na-ion Batteries

Battery electrodes materials undergo significant mechanical instabilities which affects their longevity and exert rate-limitations during the cycling process. In this study, we investigate the rate-dependent mechanical response of sodium iron phosphate (NaFePO4, NFP) cathodes during Na intercalation via galvanostatic cycling at different rates by employing digital image correlation, electrochemical methods, and mathematical model. The mechanical behaviour of the electrode shows strong dependance on the applied scan rate. At slower rates, electrode shows asymmetrical strain generation between anodic and cathodic cycles, which is attributed to the formation of cathode-electrolyte interface layers. The electrode undergoes smaller strain generation when cycled at slower rates when the same amount of Na ions is removed or inserted into the electrode. A mathematical model was developed to predict strain evolution in the composite electrode as well as the concentration profile of the Na ions in the electrode particles. Rate-dependent and time dependent factors on the strain generation in the electrode are attributed to the capacity-dependent intercalation strains, rate-dependent mismatch strains, and time-dependent irreversible strains. The combination of in situ strain measurements with the analytical model provided new insight into the electrochemically induced mechanical deformations in Na-ion cathode electrodes.

Ozdogru, Bertan↗

A new ordered triple Hollandite: Ba{sub 1.33}Sb{sub 2.66}Al{sub 5.33}O{sub 16}

Ba{sub 1.33}Sb{sub 2.66}Al{sub 5.33}O{sub 16} is a triple Hollandite, which crystallizes in a tetragonal cell (I4/m no. 87) with a=b=9.86090(5) A and c=8.77612(6) A. Its crystal structure was characterized using electron diffraction and X-ray powder diffraction; it is isotypic to K{sub 1.33}Mg{sub 3.11}Sb{sub 4.89}O{sub 16}, K{sub 1.76}Mg{sub 3.25}Sb{sub 4.75}O{sub 16} and to K{sub 1.8}Li{sub 2.45}Sb{sub 5.55}O{sub 16}. In the rutile chains of Ba{sub 1.33}Sb{sub 2.66}Al{sub 5.33}O{sub 16}, the ordering of Al and Sb atoms into unmixed sites induces the tripling of the c parameter compared to a 'single' Hollandite structure. The Ba{sup 2+} cations are dispersed along c, in the largest tunnels on non-split and fully occupied sites. They lie into Ba-Ba pairs separated by vacancies. Their regular arrangement has been confirmed by high resolution electron microscopy. Electrochemical experiments have also been performed in Li-ion cell but no Li insertion was detected. - Graphical Abstract: The new Ba{sub 1.33}Sb{sub 2.66}Al{sub 5.33}O{sub 16} triple Hollandite has been synthesized and characterized by X-ray diffraction, electron microscopy, and cyclic voltammetry. Highlights: > Synthesis of a new barium antimonium aluminium oxide with a Hollandite structure. > X-ray diffraction, electron microscopy and cyclic voltammetry studies. > Presence of cationic vacancies but no Li insertion activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rare-earth chromium gallides RE{sub 4}CrGa{sub 12} (RE=Tb-Tm)

The ternary rare-earth-metal chromium gallides RE{sub 4}CrGa{sub 12} (RE=Tb-Tm) have been prepared by reactions of the elements at 1000 Degree-Sign C in the presence of excess gallium used as a self-flux. Their structures are derived by inserting Cr atoms into a quarter of the empty Ga{sub 6} octahedral clusters found in the parent binary gallides REGa{sub 3} (AuCu{sub 3}-type), although single-crystal X-ray diffraction studies suggest that complex superstructures may be adopted. An ideal ordered Y{sub 4}PdGa{sub 12}-type structure was successfully refined for a crystal of Dy{sub 4}CrGa{sub 12} (Pearson symbol cI34, space group Im3{sup Macron }m, Z=2, a=8.572(1) A). Magnetic measurements on single-crystal samples reveal ferromagnetic or possibly ferrimagnetic ordering for the Tb, Dy, and Er members (T{sub C}=22, 15, and 2.8 K, respectively) and antiferromagnetic ordering for the Ho member (T{sub N}=7.5 K). Band structure calculations on a hypothetical 'Y{sub 4}CrGa{sub 12}' model suggest that the Cr atoms carry no local magnetic moment. - Graphical abstract: RE{sub 4}CrGa{sub 12} is derived by inserting Cr atoms into empty Ga{sub 6} octahedral clusters present in the parent binary gallides REGa{sub 3}. Highlights: Black-Right-Pointing-Pointer RE{sub 4}MGa{sub 12} (previously known for M=Fe, Ni, Pd, Pt, Ag) has been extended to M=Cr. Black-Right-Pointing-Pointer RE{sub 4}CrGa{sub 12} compounds show predominantly ferromagnetic ordering. Black-Right-Pointing-Pointer Band structure calculations suggest that Cr atoms carry no local magnetic moment.

36 MATERIALS SCIENCE↗

Design and construction of porous metal-organic frameworks based on flexible BPH pillars

Three metal-organic frameworks (MOFs), [Co{sub 2}(BPDC){sub 2}(4-BPH){center_dot}3DMF]{sub n} (1), [Cd{sub 2}(BPDC){sub 2}(4-BPH){sub 2}{center_dot}2DMF]{sub n} (2) and [Ni{sub 2}(BDC){sub 2}(3-BPH){sub 2} (H{sub 2}O){center_dot}4DMF]{sub n} (3) (H{sub 2}BPDC=biphenyl-4,4 Prime -dicarboxylic acid, H{sub 2}BDC=terephthalic acid, BPH=bis(pyridinylethylidene)hydrazine and DMF=N,N Prime -dimethylformamide), have been solvothermally synthesized based on the insertion of heterogeneous BPH pillars. Framework 1 has 'single-pillared' MOF-5-like motif with inner cage diameters of up to 18.6 A. Framework 2 has 'double pillared' MOF-5-like motif with cage diameters of 19.2 A while 3 has 'double pillared' 8-connected framework with channel diameters of 11.0 A. Powder X-ray diffraction (PXRD) shows that 3 is a dynamic porous framework. - Graphical abstract: By insertion of flexible BPH pillars based on 'pillaring' strategy, three metal-organic frameworks are obtained showing that the porous frameworks can be constructed in a much greater variety. Highlights: Black-Right-Pointing-Pointer Frameworks 1 and 2 have MOF-5 like motif. Black-Right-Pointing-Pointer The cube-like cages in 1 and 2 are quite large, comparable to the IRMOF-10. Black-Right-Pointing-Pointer Framework 1 is 'single-pillared' mode while 2 is 'double-pillared' mode. Black-Right-Pointing-Pointer PXRD and gas adsorption analysis show that 3 is a dynamic porous framework.

36 MATERIALS SCIENCE↗

Bismuth alloying properties in GaAs nanowires

First-principles calculations have been performed to investigate the structural, electronic and optical properties of bismuth alloying in GaAs nanowires. A typical model of Ga{sub 31}As{sub 31} nanowires is introduced for its reasonable band gap. The band gap of GaAs{sub 1−x}Bi{sub x} shrinks clearly with the increasing Bi concentration and the band edge shifts when spin–orbit coupling (SOC) is considered. The insertion of Bi atom leads to hybridization of Ga/As/Bi p states which contributes a lot around Fermi level. Scissor effect is involved. The optical properties are presented, including dielectric function, optical absorption spectra and reflectivity, which are also varied with the increasing of Bi concentrations. - Graphical abstract: Top view of Bi-doped GaAs nanowires. Ga, As, and Bi atoms are denoted with grey, purple and red balls, respectively. Display Omitted - Highlights: • A typical model of Ga{sub 31}As{sub 31} nanowires is introduced for its reasonable band gap. • The band gap of GaAs{sub 1−x}Bi{sub x} shrinks clearly with the increasing Bi concentration. • The band edge shifts when spin–orbit coupling (SOC) is considered. • The insertion of Bi atom leads to hybridization of Ga/As/Bi p states.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and investigation of proton conductivity for intercalated kaolinite with 4-amidinopyridinium chloride

The proton-conducting materials have potential application in devices such as fuel cells. In this study, a mineral kaolinite-based proton conducting material, kaolinite-4-amidinopyridinium hydrochloride (K-4-APy–HCl), was synthesized by the intercalated compound kaolinite-4-amidinopyridine (K-4-APy) adsorbing volatilizing HCl. The thermogravimetric analysis (TG), powder X-ray diffraction (PXRD) and IR spectrum confirmed the HCl successfully inserting into the interlayer space of kaolinite and the 4-aminopyridine being protonated. The intercalation efficiency is estimated to be ca. 85.6%. With respect to K-4-APy, the interlayer space expends by 1.53 Å. The thermal decomposition mechanism was studied by PXRD and TG techniques. The K-4-APy–HCl shows proton conductivity with σ=3.379×10{sup −8} S cm{sup −1} at 373 K and E{sub a}=1.159 eV in the anhydrous condition, which are comparable to MOFs-based proton conducting materials. - Graphical abstract: The intercalated hybrid of mineral kaolinite with 4-amidinopyridinium hydrochloride is prepared to use as proton conducting material. - Highlights: • A new strategy is proposed for preparation of kaolinite-based proton conductor. • Intercalatied hybrid was prepared by sequentially inserting 4-amidinopyridine and adsorbing HCl. • The proton conductivity of intercalated hybrid is comparable to MOFs-based proton-conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg{sup 2+}), relative to lithium-ion (Li{sup +}) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg{sup 2+}, improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recent advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes. - Graphical abstract: In this short review, we present candidate materials for reversible Mg-battery cathodes that are compatible with magnesium metal in water-free electrolytes. The data suggest that soft, polarizable anions are required for reversible cycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Doping effect on the structural properties of Cu{sub 1−x}(Ni, Zn, Al and Fe){sub x}O samples (0<x<0.10): An experimental and computational study

In this work, the effect of insertion of transition metal, TM (=Ni, Zn, Al and Fe), ions in Cu{sub 1−x}TM{sub x}O samples (0<x<0.10) prepared via co-precipitation method is studied through experimental and computational methods. The analyses of X-ray diffraction (XRD) patterns using Rietveld refinement show that i) at x=0, all samples present a monoclinic crystal system with space group C2/c and ii) for increasing the TM-doping, Ni and Zn-doped samples show a small amount of spurious phases for concentrations above x=0.05. Based on these results, a defect disorder study for using atomistic computational simulations which is based on the lattice energy minimization technique is employed to predict the location of the dopant ions in the structure. In agreement with XRD data, our computational results indicate that the trivalent (Al and Fe ions) are more favorable to be incorporated into CuO matrix than the divalent (Ni and Zn ions). - Graphical Abstract: The effect of insertion of transition metal, TM (=Ni, Zn, Al and Fe), ions in Cu{sub 1−x}TM{sub x}O samples (0<x<0.10) prepared via co-precipitation method is studied through experimental and computational methods. Display Omitted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cobalt-based metal organic framework with superior lithium anodic performance

The reversible charging of a Co-1,4-benzenedicarboxylate MOF (Co-BDC MOF) prepared via an one-pot solvothermal method was studied for use as the anode in a Li-ion cell. It was found that this MOF anode provides high reversible capacities (1090 and 611 mA h g{sup −1} at current densities of 0.2 and 1 A g{sup −1}, respectively), and an impressive rate performance. Such an outstanding Li-ion storage property has not been reported previously for the LIB anodes within the MOFs category. Ex-situ X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (IR) studies of this material at different state of charge suggest that cobalt stays at Co{sup 2+} state during discharge/charge process, so that in this case Li{sup +} may be inserted into the organic moiety without the direct participation of cobalt ions. - Graphical abstract: Co-1,4-benzenedicarboxylate MOF, synthesized through a straightforward solvothermal method, shows outstanding lithium storage performance. - Highlights: • Co-1,4-benzenedicarboxylate MOF is synthesized by a one-pot solvothermal method. • Reversible capacity of 1090 mA h g{sup −1} is achieved at a current density of 200 mA g{sup −1}. • Reversible capacity of 611 mA h g{sup −1} is achieved at a current density of 1 A g{sup −1}. • Li-ions may be inserted into the organic moieties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tailoring the interfacial microstructure and mechanical strength of SiC ceramic joints using joining temperature and interlayer thickness

Highlights: • Bonding temperature could be decreased from 1600 °C to 1300 °C by inserting the Ti foil between SiC and Ta-5W. • The initial thickness interlayer and the number of interlayer had a significant influence on interface bonding. • Layered reaction layers consisting of carbides and silicide formed at the SiC/Ti/Ta-5W interfaces. • The joint strength depended mainly on the reaction layer thickness, especially the thickness of silicide layer. - Abstract: Silicon carbide ceramic joints solid state diffusion bonded by spark plasma sintering with Ti/Ta-5W/Ti multi-interlayer in the temperature range from 1250 °C to 1500 °C were investigated in detail in terms of interfacial microstructure, elemental diffusion, phase constituents, shear strength, and fracture morphology. Layered reaction layers consisting of carbides (TiC, Ti{sub 3}SiC{sub 2}, (Ta,Ti,W)C), silicide ((Ta,Ti,W){sub 5}Si{sub 3}) and Ta-rich solid solution (Ta,Ti,W) formed at the SiC/Ti/Ta-5W interfaces. It was found that joining temperature could be decreased from 1600 °C to 1300 °C by inserting the Ti foil between SiC and Ta-5W. Nevertheless, an attempt to further decrease the joining temperature to 1250 °C failed even using a thin Ti foil. The initial thickness interlayer and the number of interlayer had an influence on the interfacial diffusion bonding at SiC/Ti interface. Higher joining temperature was needed to achieve a tough interface joining for a thick interlayer compared with a thin interlayer. The increase of interlayer number also required higher joining temperature. The shear strength reached 123.5 ± 25.3 MPa for the joint diffusion bonded at 1300 °C.

36 MATERIALS SCIENCE↗

Characterisation of chemically lithiated heat-treated electrolytic manganese dioxide

Highlights: ► Manganese oxides are a promising cathode material for lithium ion batteries. Here we examine the structural and morphological changes that occur upon reduction, and assess its impact on material performance. ► Upon reduction, MnO{sub 2} transforms into LiMn{sub 2}O{sub 4}, which is subsequently reduced to Li{sub 2}Mn{sub 2}O{sub 4}. ► Significant morphological changes occur, particularly to the material porosity. ► This transformation for MnO{sub 2} has not been reported previously. -- Abstract: Heat treated manganese dioxide is partially lithiated using butyl-lithium to determine the changes in crystal structure, chemical composition and morphology upon reduction, as a means of simulating its discharge behaviour in a non-aqueous battery cathode. As reduction proceeds, and lithium ions are inserted into the heat treated electrolytic manganese dioxide (EMD) structure, the material undergoes a phase transition to LiMn{sub 2}O{sub 4}. This new phase is further reduced to Li{sub 2}Mn{sub 2}O{sub 4}. Reduction initially results in a 56% decrease in the surface area of the material; however, at higher degrees of reduction a slight increase in this value is observed, as a consequence of the strain placed on the lattice through continued lithium insertion.

36 MATERIALS SCIENCE↗

Influence of composition modification on Ca{sub 0.5−x}Mg{sub x}Ti{sub 2}(PO{sub 4}){sub 3} (0.0 ≤ x ≤ 0.5) nanoparticles as electrodes for lithium batteries

Graphical abstract: - Highlights: • Cation mixing was determined in the Ca{sub 0.5−x}Mg{sub x}Ti{sub 2}(PO{sub 4}){sub 3} biphasic series. • Nanometric Ca{sub 0.15}Mg{sub 0.35}Ti{sub 2}(PO{sub 4}){sub 3} delivered 138 mAh/g at C/20 in lithium cells. • Low content of Ca{sup 2+} increases cell volume favoring Li{sup +} insertion in R-3c framework. • Diminution of R{sub SEI} and R{sub CT} for Ca{sub 0.15}Mg{sub 0.35}Ti{sub 2}(PO{sub 4}){sub 3} discharged electrodes. • Fast electrode response for x = 0.35. - Abstract: The Ca{sub 0.5−x}Mg{sub x}Ti{sub 2}(PO{sub 4}){sub 3} series (0.0 ≤ x ≤ 0.5) was prepared by a sol–gel method. X-ray diffraction patterns showed two rhombohedral phases which coexist for intermediate compositions. Despite of the absence of a solid solution mechanism for the whole stoichiometry range, an appreciable cation mixing was observed in both phases. {sup 31}P MAS NMR spectroscopy revealed that low magnesium contents are incorporated to the calcium compound inducing changes in the ordering of the alkaline earth cations in M{sub 1} sites. Derivative plots of the voltage–capacity curves revealed two reversible regions ascribed to the reduction of Ti{sup 4+} to Ti{sup 3+}, ascribable to the subsequent insertion of lithium ions into M{sub 1} and M{sub 2} vacant sites. Capacity values as high as 138 mAh/g after the first discharge were monitored for nanometric Ca{sub 0.15}Mg{sub 0.35}Ti{sub 2}(PO{sub 4}){sub 3} at C/20. Cell cycling under successive kinetic rates revealed a good capacity retention for samples with x = 0.15 and 0.25. Impedance spectra were recorded in lithium cells discharged after different number of cycles at different C rates. The increase in charge transfer resistance was shown to be an important factor determining the electrode behavior on extended cycling.

36 MATERIALS SCIENCE↗

Nickel/carbon core/shell nanotubes: Lanthanum nickel alloy catalyzed synthesis, characterization and studies on their ferromagnetic and lithium-ion storage properties

Highlights: • Ni/CNTs core/shell structure was synthesized using LaNi{sub 5} alloy catalyst by CVD. • The magnetic and lithium-ion storage properties of Ni/CNTs structure were studied. • The specific Ni/CNTs structure shows strong ferromagnetic property with large coercivity value of 446.42 Oe. • Ni/CNTs structure shows enhanced electrochemical performance in terms of stable capacity and better rate capability. - Abstract: A method was developed to synthesize ferromagnetic nickel core/carbon shell nanotubes (Ni/CNTs) by chemical vapor deposition using Pauli paramagnetic lanthanum nickel (LaNi{sub 5}) alloy both as a catalyst and as a source for the Ni-core. The Ni-core was obtained through oxidative dissociation followed by hydrogen reduction during the catalytic growth of the CNTs. Transmission electron microscopy (TEM), selected area electron diffraction (SAED) and X-ray diffraction (XRD) analyses reveal that the Ni-core exists as a face centered cubic single crystal. The magnetic hysteresis loop of Ni/CNTs particle shows increased coercivity (446.42 Oe) than bulk Ni at room temperature. Furthermore, the Ni/CNTs core/shell particles were investigated as anode materials in lithium-ion batteries. The Ni/CNTs electrode delivered a high discharge capacity of 309 mA h g{sup −1} at 0.2 C, and a stable cycle-life, which is attributed to high structural stability of Ni/CNTs electrode during electrochemical lithium-ion insertion and de-insertion redox reactions.

36 MATERIALS SCIENCE↗

A novel iron phosphate/oxygen hybrid cathode with high power output for the aprotic lithium-oxygen battery

Highlights: • This study affords a new strategy to improve the power output of Li-O{sub 2} cell. • FePO{sub 4}@C nanorods with exposed {010} facets are prepared and applied in O{sub 2} cathode. • Hybrid cathode retains high energy output via ORR. • Hybrid cathode attains 8-fold increased power output via Li{sup +}-insertion of FePO{sub 4}. - Abstract: The aprotic lithium-oxygen (Li-O{sub 2}) battery has recently attracted the worldwide attention by virtue of its super-large energy output. However, the extremely poor power output is one of the key issues which severely restrict the commercialization of the Li-O{sub 2} technology. In this work, we demonstrate a novel and simple strategy to address the power issue of the aprotic Li-O{sub 2} battery. An iron phosphate/oxygen (FePO{sub 4}/O{sub 2}) hybrid cathode is proposed for the first time by simply introducing the {010}-oriented FePO{sub 4} nanorods into a conventional O{sub 2} cathode. The as-built hybrid cathode not only retains a high-energy output via the O{sub 2} cathodic reaction, but also achieves an 8-fold increased power output via the Li{sup +}-insertion reaction of the {010}-oriented FePO{sub 4} nanorods.

36 MATERIALS SCIENCE↗

The GdF3 phosphors with enhanced multicolor luminescence via multi-channel excitation and energy migration procedure

Highlights: • Core-shell structured GdF{sub 3} phosphors were synthesized by hydrothermal method. • SiO{sub 2} coating layers prevent aggregation and sintering during thermal annealing. • The annealed CSS nanophosphors were highly dispersible. • The inserted PMA significantly enhances multicolor luminescence. • The annealed CSS phosphors exhibit enhanced multicolor luminescence properties. - Abstract: A collection of GdF{sub 3} core-shell structured (CSS) phosphors were synthesized by hydrothermal method. The as-prepared (AP) phosphors were coated with SiO{sub 2} layers to avoid aggregation and sintering during thermal annealing at 800 °C, after which the SiO{sub 2} layers were etched off and the annealed phosphors became highly dispersible. The annealed CSS phosphor aGdF{sub 3}:Eu{sup 3+}@GdF{sub 3}:Ce{sup 3+},Dy{sup 3+} shows excellent multicolor luminescence performance with the aid of dual-channel excitation and energy migration (EM) procedure of Gd{sup 3+} ions. By inserting pyromellitic acid (PMA) organic ligands into the interfaces between annealed core and AP shell layer regions, the so-called antenna effect of organic ligands of PMA forms a new excitation channel, which makes the CSS phosphor aGdF{sub 3}:Eu{sup 3+}@PMA@GdF{sub 3}:Ce{sup 3+},Dy{sup 3+} exhibit significantly enhanced multicolor luminescence via multi-channel excitation and EM process. The prepared CSS phosphors in this work are excellent candidates for applications in solid-state lighting.

36 MATERIALS SCIENCE↗

Effects of channel thickness on structure and transport properties of AlGaN/InGaN heterostructures grown by pulsed metal organic chemical vapor deposition

Highlights: • High quality AlGaN/InGaN heterostructures are grown and the effects of InGaN channel thickness on the structural and transport properties are investigated in detailed. • A high electron mobility of 1712 cm{sup 2}/Vis achieved for the heterostructures with an optimum channel thickness of 21 nm, indicating the huge potential of InGaN channel heterostructures in high frequency and high power applications. • The analyze method in this work can be generalized to both the studies of InGaN channel heterostructures with arbitrary component and all the heterostructures with inserted channel. - Abstract: High-quality AlGaN/InGaN heterostructures are grown and the effects of InGaN channel thickness on the structure and transport properties are investigated. With the increase of InGaN channel thickness from 7 nm to 28 nm, the two-dimensional electron gas density decreases continuously, while the mobility shows a trend of increasing at first, and then decreasing. The optimum thickness of 21 nm is obtained for the In{sub 0.05}Ga{sub 0.95}N channel, achieving a high electron mobility of 1712 cm{sup 2}/V, which indicates the huge potential for InGaN channel heterostructures in high-frequency and high-power applications. The variation in transport properties is studied by analyzing the structure formation, material quality, and interface characteristic in detail. The results are not only beneficial for the further study of the InGaN channel heterostructures, but also instructive for the other inserted channel system.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A rationally designed polysulfide-trapping interface on the polymeric separator for high-energy Li–S batteries

A coating layer consisting of a layer of graphene oxide (GO) inserted in between two layers of multi-walled carbon nanotubes (MWCNT) forms a multifunctional polysulfide-trapping triple-interface on the polymeric separator for lithium–sulfur (Li–S) batteries. The top and bottom highly conductive MWCNT interfaces are able to physically inhibit polysulfide diffusion and effectively reutilize the trapped active material during cycling. The inserted ultrathin GO layer with negatively charged carboxyl groups, on the other hand, electrostatically repels the migrating polysulfide anions. The stacked GO sheets also extensively prolong the migration routes of the polysulfides. Additionally, the “buffer zones” interspersed within the triple-interface accommodate the migrating polysulfides. Thus, the sandwiched separators enable Li–S cells with a high-sulfur-loading (10 mg cm -2 ), high areal capacity (10.9 mA h cm -2 ), and stable cycling ability even though the coating layer is ultra-thin (~17 μm) and light-weight (~0.23 mg cm -2 ).

25 ENERGY STORAGE↗

NASICON-type Na 3 Fe 2 (PO 4 ) 3 as a low-cost and high-rate anode material for aqueous sodium-ion batteries

Aqueous sodium-ion batteries are attractive battery alternatives for stationary energy storage due to their inherently low cost and high safety. The development of advanced electrode materials with excellent performance and low cost is crucial for the success of aqueous Na-ion batteries. Albeit the high capacity and stable cycling of the leading anode of NaTi 2 (PO 4 ) 3 , the high price of titanium element and the low Na-insertion potential close to the hydrogen evolution reaction may plague its application. Here we introduced a NASICON-type Na 3 Fe 2 (PO 4 ) 3 as a promising anode alternative for aqueous Na-ion batteries. Synchrotron X-ray diffraction and spectroscopy confirm its phase and atomic structure. Electrochemical characterization and X-ray photoelectron spectroscopy reveal the reversible Na+ insertion in Na 3 Fe 2 (PO 4 ) 3 due to the Fe 3+ /Fe 2+ redox couple, which renders a specific capacity of ~60 mAh g -1 and excellent cycling of 1000 cycles at 10C rate. A Super high rate of 100C was also achieved for this anode with a capacity retention of 61% after 1000 cycles. In addition, the Na 3 Fe 2 (PO 4 ) 3 anode is paired with a Prussian white analogue of Na 2 Mn[Fe(CN) 6 ] into a full cell, exhibiting promising cell performance and material sustainability. Furthermore, our work underlines the importance of fabricating aqueous batteries on the basis of the Earth-abundant, cost-effective, and non-toxic elements.

25 ENERGY STORAGE↗