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 sa...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.展开更多
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 pest...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.展开更多
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 s...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.展开更多
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...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.展开更多
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 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.展开更多
Exploring high-performance electrode materials are indispensable for the commercialization of potassiumion batteries(PIBs).Nickel thiophosphate(NPS),a representative ternary metal thiophosphate,holds great promise as ...Exploring high-performance electrode materials are indispensable for the commercialization of potassiumion batteries(PIBs).Nickel thiophosphate(NPS),a representative ternary metal thiophosphate,holds great promise as an anode due to its high theoretical capacity and distinctive layered structure,yet still facing critical challenges such as rapid capacity decay and sluggish rate performance.Herein,we developed a flexible,self-supporting composite film anode by integrating high-purity NPS nanosheets within a three-dimensional(3D) conductive scaffold composed of nitrogen-doped graphene(NG) and single-wall carbon nanotube(SWNT) via simple vacuum filtration method.The resulting hybrid film features abundant heterointerfaces,which enhance electron/ion transport,accommodate volume changes,and stabilize the electrode structure.As a result,the anode delivers high potassium storage capacity of 643.5 mAh g^(-1) at 0.1 A g^(-1)and maintains 163.9 mAh g^(-1) at 10 A g^(-1),showcasing excellent rate performance.Full cell assemblies exhibit stable cycling performance with a reversible capacity of 207.8 mAh g^(-1) after 100 cycles.Combined crystallography and valence state analyses reveal a disordered phase transition in crystalline NPS during potassiation,indicating a dual mechanism involving both conversion and alloying reactions.This study offers valuable insights into the rational design of advanced anode materials for next-generation PIBs.展开更多
Exploring new potential infrared(IR)birefringent crystals is important for modulating the polarization of light in optical communication,but the rational structural design for the enhancement of optical anisotropy is ...Exploring new potential infrared(IR)birefringent crystals is important for modulating the polarization of light in optical communication,but the rational structural design for the enhancement of optical anisotropy is still a great challenge.展开更多
The exploration of new infrared(IR)nonlinear optical(NLO)crystals with large second-harmonic generation(SHG)responses and high laser-induced damage thresholds(LIDTs)concurrently is urgently needed and challenging.Here...The exploration of new infrared(IR)nonlinear optical(NLO)crystals with large second-harmonic generation(SHG)responses and high laser-induced damage thresholds(LIDTs)concurrently is urgently needed and challenging.Herein,the first-type of noncentrosymmetric(NCS)alkali metal Ag-based thiophosphates KAg_(2)PS_(4)(1)and(Na_(0.30)K_(0.70))Ag_(2)PS_(4)(2)were successfully synthesized using a high-temperature solid-state method.展开更多
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 volu...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.展开更多
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 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.展开更多
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 soli...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.展开更多
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,...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.展开更多
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 diffra...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.展开更多
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-di...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.展开更多
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 ...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.展开更多
A non-centrosymmetric metal-free thiophosphate,γ-P_(4)S_(3)I_(2),was successfully synthesized utilizing polymorphism strategy in this study.γ-P_(4)S_(3)I_(2)crystallized in the space group of P4_(3)and featured para...A non-centrosymmetric metal-free thiophosphate,γ-P_(4)S_(3)I_(2),was successfully synthesized utilizing polymorphism strategy in this study.γ-P_(4)S_(3)I_(2)crystallized in the space group of P4_(3)and featured paralleled(P_(4)S_(3)I_(2))_(n)molecular clusters.Importantly,it exhibited promising nonlinear optical(NLO)performances,such as a phase-matchable second harmonic generation(SHG)efficiency(0.5×AgGaS_(2)),wide band gap(2.38 eV),large birefringence(0.118@2050 nm),and wide infrared transparency,suggesting thatγ-P_(4)S_(3)I_(2)may be a potential IR NLO candidate.展开更多
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,the...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.展开更多
The dependence of nonlinear optical absorption and carrier dynamics on the thickness of chromium thiophosphate (CrPS_(4))is investigated.Utilizing the I-scan system,we have observed the typical two-photon absorption (...The dependence of nonlinear optical absorption and carrier dynamics on the thickness of chromium thiophosphate (CrPS_(4))is investigated.Utilizing the I-scan system,we have observed the typical two-photon absorption (TPA) at 780 nm for three different thicknesses.The TPA coefficient,third-order nonlinear optical susceptibility Imχ^((3)),and the figure of merit have been obtained by fitting the I-scan data.Using nondegenerate pump-probe measurements,the photoinduced absorption has been observed,and the carrier relaxation processes are phonon-assisted.This study provides deep insights into the nonlinear optical properties of CrPS_(4),which is of great significance for potential applications in ultrafast optical devices.展开更多
文摘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.
文摘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.
基金the Natural Science Foundation of China(No.22105218).
文摘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.
基金the financial support by the NSF of China(21701176)the National Postdoctoral Program for Innovative Talents(BX201600163)the China Postdoctoral Science Foundation(2016M600510)
文摘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.
文摘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.
基金financially supported by the National Natural Science Foundation of China(Nos.52273081,22278329,52573093,and 92472124)the Natural Science Foundation of Shaanxi Province(No.2021GXLH-Z-075)+1 种基金the High-Level Innovation and Entrepreneurship Talent Project of Qinchuangyuan(No.OCYRCXM-2022-308)the State Key Laboratory for Electrical Insulation and Power Equipment(No.EIPE23125)
文摘Exploring high-performance electrode materials are indispensable for the commercialization of potassiumion batteries(PIBs).Nickel thiophosphate(NPS),a representative ternary metal thiophosphate,holds great promise as an anode due to its high theoretical capacity and distinctive layered structure,yet still facing critical challenges such as rapid capacity decay and sluggish rate performance.Herein,we developed a flexible,self-supporting composite film anode by integrating high-purity NPS nanosheets within a three-dimensional(3D) conductive scaffold composed of nitrogen-doped graphene(NG) and single-wall carbon nanotube(SWNT) via simple vacuum filtration method.The resulting hybrid film features abundant heterointerfaces,which enhance electron/ion transport,accommodate volume changes,and stabilize the electrode structure.As a result,the anode delivers high potassium storage capacity of 643.5 mAh g^(-1) at 0.1 A g^(-1)and maintains 163.9 mAh g^(-1) at 10 A g^(-1),showcasing excellent rate performance.Full cell assemblies exhibit stable cycling performance with a reversible capacity of 207.8 mAh g^(-1) after 100 cycles.Combined crystallography and valence state analyses reveal a disordered phase transition in crystalline NPS during potassiation,indicating a dual mechanism involving both conversion and alloying reactions.This study offers valuable insights into the rational design of advanced anode materials for next-generation PIBs.
基金supported by the National Natural Science Foundation of China(Grant No.52372009 and 52272004)and the Qilu Young Scholar Program of Shandong University.
文摘Exploring new potential infrared(IR)birefringent crystals is important for modulating the polarization of light in optical communication,but the rational structural design for the enhancement of optical anisotropy is still a great challenge.
基金support by the National Natural Science Foundation of China(21771159,22071212)the Qinglan Project of Jiangsu Province of China,the Youth Innovation Promotion Association of Chinese Academy of Sciences(2022303)the Foundation of Excellent Doctoral Dissertation of Yangzhou University.
文摘The exploration of new infrared(IR)nonlinear optical(NLO)crystals with large second-harmonic generation(SHG)responses and high laser-induced damage thresholds(LIDTs)concurrently is urgently needed and challenging.Herein,the first-type of noncentrosymmetric(NCS)alkali metal Ag-based thiophosphates KAg_(2)PS_(4)(1)and(Na_(0.30)K_(0.70))Ag_(2)PS_(4)(2)were successfully synthesized using a high-temperature solid-state method.
基金This study was supported by BASF SE.F Strauss acknowledges financial support from the Fonds der Chemischen Industrie through a Liebig fellowship.
文摘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.
基金supported by the NSF of China(21827813,21921001,22075283)Scientific Research Fund of Natural Science Foundation of Fujian Province(2020J01115)the Youth Innovation Promotion Association of CAS(No.20200303)。
文摘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.
基金the financial support from the National Natural Science Foundation of China(Nos.91963118,51801030)supported by the Open Project Program of Key Laboratory of Preparation and Application of Environmental Friendly Materials(Jilin Normal University,No.2020004)。
文摘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.
基金financially supported by the Key Grant for Special Professors in Jiangsu Province(No.RK030STP18001)the Scientific Research Foundation of Nanjing University of Posts and Telecommunications(No.NY218150)“1311 Talents Program”of Nanjing University of Posts and Telecommunications and the National Postdoctoral Program for Innovative Talents(No.BX20190156)。
文摘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.
文摘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.
基金Financial supports from the National Natural Science Foundation of China(22265018 and 21961019)the Key Project of Natural Science Foundation of Jiangxi Province(20232ACB204010)。
文摘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.
基金the National Natural Science Foundation of China(12025503,U1867215,11875211,U1932134)Hubei Provincial Natural Science Foundation(2019CFA036)the Fundamental Research Funds for the Central Universities(2042020kf0211)。
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.22222510,21975255 and 21921001)Natural Science Foundation of Fujian Province(2021J01514)+2 种基金the Foundation of Fujian Science&Technology Innovation Laboratory(2021ZR202)Youth Innovation Promotion Association CAS(2019303)Open Project of State Key Laboratory of Crystal Materials,Shandong University(KF1907).
文摘A non-centrosymmetric metal-free thiophosphate,γ-P_(4)S_(3)I_(2),was successfully synthesized utilizing polymorphism strategy in this study.γ-P_(4)S_(3)I_(2)crystallized in the space group of P4_(3)and featured paralleled(P_(4)S_(3)I_(2))_(n)molecular clusters.Importantly,it exhibited promising nonlinear optical(NLO)performances,such as a phase-matchable second harmonic generation(SHG)efficiency(0.5×AgGaS_(2)),wide band gap(2.38 eV),large birefringence(0.118@2050 nm),and wide infrared transparency,suggesting thatγ-P_(4)S_(3)I_(2)may be a potential IR NLO candidate.
基金supported by the U.S.Department of Energy’s Office of Energy Efficiency and Renewable Energy(EERE)under the Vehicle Technologies Program under Contact DE-EE0008864.
文摘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.
基金supported by the National Natural Science Foundation of China (Nos.82227806,12227901,and 12274280)the Strategic Priority Research Program of Chinese Academy of Sciences (No.XDB43010200)the National Key Research and Development Program of China (No.2022YFA1404603)。
文摘The dependence of nonlinear optical absorption and carrier dynamics on the thickness of chromium thiophosphate (CrPS_(4))is investigated.Utilizing the I-scan system,we have observed the typical two-photon absorption (TPA) at 780 nm for three different thicknesses.The TPA coefficient,third-order nonlinear optical susceptibility Imχ^((3)),and the figure of merit have been obtained by fitting the I-scan data.Using nondegenerate pump-probe measurements,the photoinduced absorption has been observed,and the carrier relaxation processes are phonon-assisted.This study provides deep insights into the nonlinear optical properties of CrPS_(4),which is of great significance for potential applications in ultrafast optical devices.
