Two-dimensional layered In_(2)P_(3)S_(9): A novel superior anode material for sodium-ion batteries

Developing reliable and efficient anode materials is essential for the successfully practical application of sodium-ion batteries.Herein,employing a straightforward and rapid chemical vapor deposition technique,two-dimensional layered ternary indium phosphorus sulfide(In_(2)P_(3)S_(9)) nanosheets are prepared.The layered structure and ternary composition of the In_(2)P_(3)S_(9) electrode result in impressive electrochemical performance,including a high reversible capacity of 704 mA h g^(-1) at 0.1 A g^(-1),an outstanding rate capability with 425 mA h g^(-1) at 5 A g^(-1),and an exceptional cycling stability with a capacity retention of88% after 350 cycles at 1 A g^(-1).Furthermore,sodium-ion full cell also affords a high capacity of 308 and114 mA h g^(-1) at 0.1 and 5 A g^(-1).Ex-situ X-ray diffraction and ex-situ high-resolution transmission electron microscopy tests are conducted to investigate the underlying Na-storage mechanism of In_(2)P_(3)S_(9).The results reveal that during the first cycle,the P-S bond is broken to form the elemental P and In_(2)S_(3),collectively contributing to a remarkably high reversible specific capacity.The excellent electrochemical energy storage results corroborate the practical application potential of In_(2)P_(3)S_(9) for sodium-ion batteries.

Electronic Coupling of Single Atom and FePS_3 Boosts Water Electrolysis

Engineering the electronic structure of surface active sites at the atomic level can be an efficient way to modulate the reactivity of catalysts.Herein,we report the rational tuning of surface electronic structure of FePS_(3) nanosheets(NSs)by anchoring atomically dispersed metal atom.Theoretical calculations predict that the strong electronic coupling effect in single-atom Ni-FePS_(3) facilitates electron aggregation from Fe atom to the nearby Ni-S bond and enhances the electron-transfer of Ni and S sites,which balances the oxygen species adsorption capacity,reinforces water adsorption and dissociation process to accelerate corresponding oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).The optimal Ni-FePS_(3)NSs/C exhibits outstanding electrochemical water-splitting activities,delivering an overpotential of 287 mV at the current density of 10 mA cm^(-2) and a Tafel slope of 41.1 mV dec^(-1) for OER;as well as an overpotential decrease of 219 mV for HER compared with pure FePS_(3)NSs/C.The concept of electronic coupling interaction between the substrate and implanted single active species offers an additional method for catalyst design and beyond.

Extraction of aurum(III) with thiophosphate

The extraction capability of auram with di-(2-ethylhexyl)monothiophosphoricacid from hydrochloric acid solution has been studied. The extraction capability decreases with theincrease of acidity. It is showed by the saturation method and equal Moore series method that thecomposition of the extraction complex is AuR_3. IR and ~1H NMR studies indicate that the extractionmechanism is a cation exchange process through coordination with P=S bonds.

Highly Efficient Degradation of Thiophosphate Pesticides Catalyzed by Cyclopalladated Ferrocenylketimines

In this paper, four functional substituted derivatives of cyclopalladated ferrocenyl- ketimines 1~4, which were as mimetics of metal-dependent esterases for catalyzing the hydrolysis of thiophosphoric acid esters pesticides, were synthesized and characterized. All the four cyclopalladated complexes can efficiently catalyze the degradation of thiophosphoric acid pesticides, such as methyl parathion. The Pd catalyst with coordinated oxime is more active and exhibits an increased selectivity towards sulfur containing pesticides.

Preparation and Structural Chemistry of a Series of Rare Earth Compounds REPS_4

The thiophosphates of the rare earths REPS 4(RE=Y, La～Lu) were prepared by solid state reaction. Their unit cell parameters and the structures of HoPS 4, ErPS 4 and TmPS 4 were determined by X ray powder diffraction. All REPS 4(RE=Y, La～Yb) crystallize in the tetragonal space group I4 1/acd , a ≈1 1 nm, c ≈1 9 nm, Z =16 . Each RE 3+ is surrounded by eight sulfurs and thus forms a distorted tetragonal antiprism. This kind of structures has significant Van Der Waals′ vacant space with a diameter of about 0 625 nm along c axis and of 0 35 nm along a and b axis. But LuPS 4 crystallizes in a monoclinic structure which is most probably layered. The influence of lanthanide contraction on the stability of the tetragonal REAX 4 structure was studied and a criterion for the existence of the tetragonal structure in the REAX 4 series compounds is proposed. There is 2 4 d A X / r 1 9.

Synthesis,Crystal Structure and Magnetic Properties of the New Quaternary Thiophosphate Rb_2FeP_2S_6

A new quaternary thiophosphate Rb_2FeP_2S_6 was synthesized by the alkali metal halide flux method.The compound crystallizes in the monoclinic space group P2_1/c（No.14） with a = 6.042（3）,b = 12.338（6）,c = 9.045（4） ？,b = 124.25（2）°,V = 557.3（5） ？~3 and Z = 2.Its structure features 1-D infinite _∞~1[FeP_2S_6]^（2-） chains and counter cations Rb~＋.It shows a band gap of 2.03 eV.The nearest intra-chain Fe^（2＋） cations are antiferromagnetically coupled with each other,and there are weak ferromagnetic-like interactions between neighboring _∞1[FeP_2S_6]（2-） chains,resulting in two successive magnetic phase transitions.

Raman Spectroscopy of a Series of the Rare Earth Thiophosphate(LnPS4,Ln=Y,La～Lu)

The Raman spectroscopy study of LnPS 4 series compounds with tetragonal xenotime structure shows that the symmetrical stretching vibration frequency ν 1 increases linearly with the lanthanide contraction, i.e., the decrease of the effective ionic radius r Ln 3+ ; moreover, the ν 1 frequency for the non tetragonal LuPS 4 falls off the line running through the corresponding values for the tetragonal phases. This observation is consistent with their structural chemistry modifications.

Crystal Structure of N-(N-Phenylthiazotone)imino-O-ethyl-N-isopropylaminothiophosphate

C_(14)H_(20)N_3O_2PS_2, M_r = 357. 44, monoclinic, space group P21/c, a =10. 825(2) . b=10. 511(2) , c=16. 402(1) ,β=102. 12(1)°,V=1824. 8 ￣3 . Z=4, D_x= 1. 30 g/cm￣3 , μ=3. 74 cm￣(-1), and F(000) = 376. R(R_w) is 0. 051 (0. 063) for1599 observed unique reflections.The five-membered thiazolinone is planar group. andthe dihedral angle between it and the six-membered phenyl is 64. 2°.

The compatibly large nonlinear optical effect and high laser-induced damage threshold in a thiophosphate CsInP_(2)S_(7)constructed with[P_(2)S_(7)]^(4-)and[InS_(6)]^(9-)

It is challenging to cooperatively improve the nonlinear optical(NLO)efficiency and the laser-induced damage threshold(LIDT).This work reports a novel IR NLO materials CsInP_(2)S_(7)(CIPS)designed by combination the strategies of alkali metals substitution and microscopic NLO units PS4 introduction based on AgGaS_(2).CIPS was composed of strongly distorted[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers constructed by corner-sharing[PS_(4)]^(3-),which increase the NLO efficiency and decrease thermal expansion anisotropy simultaneously.Compared with AgGaS_(2),CIPS exhibited strong phase matchable NLO response ca.1.1×AGS@2.1μm,high LIDT ca.20.8×AgGaS_(2),and IR transparency up to 15.3μm.Structural analysis and theoretical investigation confirmed that large SHG effect and ultrahigh LIDT of CIPS originated from the synergistic contribution of[InS_(6)]^(9-)octahedra and[P_(2)S_(7)]4-dimers.These results indicate that CIPS is a promising NLO candidate in the mid-IR region,and this study provides a new approach for developing potential NLO-LIDT compatible materials.

Phase engineering two-dimensional nanostructures for electrocatalytic hydrogen evolution reaction

Hydrogen(H2)is considered to be a promising substitute for fossil fuels.Two-dimensional(2D)nanomaterials have exhibited an efficient electrocatalytic capacity to catalyze hydrogen evolution reaction(HER).Particularly,phase engineering of 2D nanomaterials is opening a novel research direction to endow 2D nanostructures with fascinating properties for deep applications in catalyzing HER.In this review,we briefly summarize the research progress and present the current challenges on phase engineering of 2D nanomaterials for their applications in electrocatalytic HER.Our summary will be of significance to provide fundamental understanding for designing novel 2D nanomaterials with unconventional phases to electrochemically catalyze HER.

Impact of fabrication methods on binder distribution and charge transport in composite cathodes of all-solid-state batteries

The manufacturing process of all-solid-state batteries necessitates the use of polymer binders.However,these binders,being ionic insulators by nature,can adversely affect charge transport within composite cathodes,thereby impacting the rate performance of the batteries.In this work,we aim to investigate the impact of fabrication methods,specifically the solvent-free dry process versus the slurry-cast wet process,on binder distribution and charge transport in composite cathodes of solid-state batteries.In the dry process,the binder forms a fibrous network,while the wet process results in binder coverage on the surface of cathode active materials.The difference in microstructure leads to a notable 20-fold increase in ionic conductivity in the dry-processed cathode.Consequently,the cells processed via the dry method exhibit higher capacity retention of 89%and 83%at C/3 and C/2 rates,respectively,in comparison to 68%and 58%for the wet-processed cells at the same rate.These findings provide valuable insights into the influence of fabrication methods on binder distribution and charge transport,contributing to a better understanding of the binder’s role in manufacturing of all-solid-state batteries.

SbPS_(4):A novel anode for high-performance sodium-ion batteries

With the in-depth research of sodium-ion batteries(SIBs),the development of novel sodium-ion anode material has become a top priority.In this work,tube cluster-shaped SbPS_(4)was synthesized by a high-temperature solid phase reaction.Then the typical short tubular ternary thiophosphate SbPS_(4)compounded with graphene oxide(SbPS_(4)/GO)was successfully synthesized after ultrasonication and freeze-drying.SbPS_(4)shows a high theoretical specific capacity(1335 mAh/g)according to the conversion-alloying dual mechanisms.The unique short tube inserted in the spongy graphene structure of SbPS_(4)/GO results in boosting the Na ions transport and alleviating the huge volume change in the charging and discharging processes,improving the sodium storage performance.Consequently,the tubular SbPS_(4)compounded with 10%GO provides an outstanding capacity of 359.58 mAh/g at 500 mA/g.The result indicates that SbPS_(4)/GO anode has a promising application potential for SIBs.

The interplay between (electro)chemical and (chemo)mechanical effects in the cycling performance of thiophosphate-based solid-state batteries

Solid-state batteries(SSBs)are a promising next step in electrochemical energy storage but are plagued by a number of problems.In this study,we demonstrate the recurring issue of mechanical degradation because of volume changes in layered Ni-rich oxide cathode materials in thiophosphate-based SSBs.Specifically,we explore superionic solid electrolytes(SEs)of different crystallinity,namely glassy 1.5Li_(2)S-0.5P_(2)S_(5)-LiI and argyrodite Li_(6)PS_(5)Cl,with emphasis on how they affect the cyclability of slurry-cast cathodes with NCM622(60%Ni)or NCM851005(85%Ni).The application of a combination of ex situ and in situ analytical techniques helped to reveal the benefits of using a SE with a low Young’s modulus.Through a synergistic interplay of(electro)chemical and(chemo)mechanical effects,the glassy SE employed in this work was able to achieve robust and stable interfaces,enabling intimate contact with the cathode material while at the same time mitigating volume changes.Our results emphasize the importance of considering chemical,electrochemical,and mechanical properties to realize long-term cycling performance in high-loading SSBs.

Synthesis,Crystal Structure and Fluorescent Properties of New Layered Thiophosphate Cs_(2)Ga_(3)PS_(8)

A new quaternary metal thiophosphate,Cs_(2)Ga_(3)PS_(8),in triclinic P1^(-) space group has been successfully synthesized by a reactive-flux method.Its structural framework is derived from well-known AM^(Ⅲ)M^(Ⅳ)Q_(4) (A=alkali metal;M^(Ⅲ)=Al,Ga,In;M^(Ⅳ)=Si,Ge,Sn;Q=S,Se) system and composed of two-dimensional ^(2)∞[Ga_(3)PS_(8)]^(2-) layers separated by Cs^(+).The compound exhibits a wide band gap of 3.08 eV and congruent-melting behavior with melt point of 645℃.Interestingly,Cs_(2)Ga_(3)PS_(8) exhibits a broad photoluminescent emission band at 420 nm upon excitation at 295 nm.Moreover,electronic structure calculations indicate that Cs_(2)Ga_(3)PS_(8) is a direct band gap compound and its luminescent process can be mainly ascribed to electron transfer from the S-3p and Ga-4p states to S-3p and P-3p.