Solid-state polymer electrolytes(SPEs)have attracted increasing attention due to good interfacial contact,light weight,and easy manufacturing.However,the practical application of SPEs such as the most widely studied p...Solid-state polymer electrolytes(SPEs)have attracted increasing attention due to good interfacial contact,light weight,and easy manufacturing.However,the practical application of SPEs such as the most widely studied poly(ethylene oxide)(PEO)in high-energy solid polymer batteries is still challenging,and the reasons are yet elusive.Here,it is found that the mismatch between PEO and 4.2 V-class cathodes is beyond the limited electrochemical window of PEO in the solid Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2)(NMC)-PEO batteries.The initial oxidation of PEO initiates remarkable surface reconstruction of NMC grains in solid batteries that are different from the situation in liquid electrolytes.Well-aligned nanovoids are observed in NMC grains during the diffusion of surface reconstruction layers towards the bulk in solid batteries.The substantial interphasial degradation,therefore,blocks smooth Li+transport across the NMC-PEO interface and causes performance degradation.A thin yet effective Li F-containing protection layer on NMC can effectively stabilize the NMC-PEO interface with a greatly improved lifespan of NMC|PEO|Li batteries.This work deepens the understanding of degradations in high-voltage solid-state polymer batteries.展开更多
In addition to the three well-known Ag-related precipitates(Ω,X′and Z)in the Al-Cu-Mg-Ag alloys,Ag can also be involved in the formation of the as-cast second phases.However,the effect of Ag ad-dition in Al-Cu-Mg-Ag...In addition to the three well-known Ag-related precipitates(Ω,X′and Z)in the Al-Cu-Mg-Ag alloys,Ag can also be involved in the formation of the as-cast second phases.However,the effect of Ag ad-dition in Al-Cu-Mg-Ag alloys has not been completely studied and even the structure of the as-cast Ag-containing phases is still controversial.By employing the focused ion beam(FIB)combined with transmis-sion electron microscopy(TEM)techniques and density functional theory(DFT)calculations,the forma-tion mechanisms of the Ag-containing phases in the as-cast Al-Cu-Mg-Ag alloys have been investigated.The Ag-containing phases are a series of hexagonal C14-type Laves phases with continuously varying Ag concentrations,described as(Al_(x)Cuy Ag_(1-x-y))_(2)Mg.Moreover,the specific occupancy sites of the atoms in(Al_(x)Cuy Ag_(1-x-y))_(2)Mg were determined.The formation of the(Al_(x)Cuy Ag_(1-x-y))_(2)Mg can be attributed to the stronger Ag-induced aggregation of solute atoms in the initial stage and the establishment of strong Ag-X(X=Al,Mg and Ag)bonding in the Ag-containing phases.Furthermore,our experiments have revealed the solidification sequence of Al-Cu-Mg-Ag alloys,and pointed out that(Al_(x)Cuy Ag_(1-x-y))_(2)Mg is formed at a lower temperature(493.9℃)through the reaction L■Al_(2)CuMg+(Al_(x)Cuy Ag_(1-x-y))_(2)Mg.The study could have positive implications for refinement of the Al-Cu-Mg-Ag quaternary phase diagram and promote the composition-property design of novel aluminum alloys based on(Al_(x)Cuy Ag_(1-x-y))_(2)Mg in the future.展开更多
Enhancing the lifetime of perovskite solar cells(PSCs)is one of the essential challenges for their industrialization.Although the external encapsulation protects the perovskite device from the erosion of moisture and ...Enhancing the lifetime of perovskite solar cells(PSCs)is one of the essential challenges for their industrialization.Although the external encapsulation protects the perovskite device from the erosion of moisture and oxygen under various harsh conditions.However,the perovskite devices still undergo static and dynamic thermal stress during thermal and thermal cycling aging,respectively,resulting in irreversible damage to the morphology,component,and phase of stacked materials.Herein,the viscoelastic polymer polyvinyl butyral(PVB)material is designed onto the surface of perovskite films to form flexible interface encapsulation.After PVB interface encapsulation,the surface modulus of perovskite films decreases by nearly 50%,and the interface stress range under the dynamic temperature field(−40 to 85°C)drops from−42.5 to 64.8 MPa to−14.8 to 5.0 MPa.Besides,PVB forms chemical interactions with FA+cations and Pb^(2+),and the macroscopic residual stress is regulated and defects are reduced of the PVB encapsulated perovskite film.As a result,the optimized device's efficiency increases from 22.21%to 23.11%.Additionally,after 1500 h of thermal treatment(85°C),1000 h of damp heat test(85°C&85%RH),and 250 cycles of thermal cycling test(−40 to 85°C),the devices maintain 92.6%,85.8%,and 96.1%of their initial efficiencies,respectively.展开更多
Metal organic frameworks(MOFs) have been extensively investigated in Li-S batteries owing to high surface area, adjustable structures and abundant catalytic sites. Nevertheless, the insulating nature of traditional MO...Metal organic frameworks(MOFs) have been extensively investigated in Li-S batteries owing to high surface area, adjustable structures and abundant catalytic sites. Nevertheless, the insulating nature of traditional MOFs render retarded kinetics of polysulfides conversion, leading to insufficient utilization of sulfur. In comparison, conductive MOFs(c-MOFs) show great potential for promoting polysulfides transformation due to superb electronic conductivity. In this work, a nickel-catecholates based c-MOF, NiHHTP(HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene), is designed to regulate surface chemistry of self-supported carbon paper for advanced Li-S batteries. Taking advantage of the porous structure and high conductivity, the as-prepared Ni-HHTP is conducive to synergising strengthening the chemisorption of polysulfides and accelerating the reaction kinetics in Li-S batteries, significantly mitigating the polysulfides diffusion from the non-encapsulated sulfur cathode, therefore promoting polysulfides transformation in Li-S batteries. This work points out a promising modification strategy for developing advanced sulfur cathode in Li-S batteries.展开更多
Nitriles as efficient electrolyte additives are widely used in high-voltage lithium-ion batteries.However,their working mechanisms are still mysterious,especially in practical high-voltage LiCoO_(2)pouch lithium-ion b...Nitriles as efficient electrolyte additives are widely used in high-voltage lithium-ion batteries.However,their working mechanisms are still mysterious,especially in practical high-voltage LiCoO_(2)pouch lithium-ion batteries.Herein,we adopt a tridentate ligandcontaining 1,3,6-hexanetricarbonitrile(HTCN)as an effective electrolyte additive to shed light on the mechanism of stabilizing high-voltage LiCoO_(2)cathode(4.5 V)through nitriles.The LiCoO_(2)/graphite pouch cells with the HTCN additive electrolyte possess superior cycling performance,90%retention of the initial capacity after 800 cycles at 25℃,and 72%retention after 500 cycles at 45℃,which is feasible for practical application.Such an excellent cycling performance can be attributed to the stable interface:The HTCN molecules with strong electron-donating ability participate in the construction of cathode-electrolyte interphase(CEI)through coordinating with Co ions,which suppresses the decomposition of electrolyte and improves the structural stability of LiCoO_(2)during cycling.In summary,the work recognizes a coordinating-based interphase-forming mechanism as an effective strategy to optimize the performance of high voltage LiCoO_(2)cathode with appropriate electrolyte additives for practical pouch batteries.展开更多
■ compression twins with high density stacking faults were studied at atomic scale using Cscorrection transmission electron microscopy. On one side of the ■ twin boundary, there were many steps arranged alternately ...■ compression twins with high density stacking faults were studied at atomic scale using Cscorrection transmission electron microscopy. On one side of the ■ twin boundary, there were many steps arranged alternately with the coherent twin boundaries. Most of the steps were linked with stacking faults inside twins. Burgers vector of twinning dislocations and the mismatch strain at steps were characterized. Due to the compressive mismatch strain at steps, the high density stacking faults inside twins were formed at twin tips during twinning process. The localized strain at the steps would be related to the crack nucleation in magnesium alloys.展开更多
Since titanium has high affinity for hydrogen and reacts reversibly with hydrogen,the precipitation of titanium hydrides in titanium and its alloys cannot be ignored.Two most common hydride precipitates in α-Ti matrix...Since titanium has high affinity for hydrogen and reacts reversibly with hydrogen,the precipitation of titanium hydrides in titanium and its alloys cannot be ignored.Two most common hydride precipitates in α-Ti matrix areγ-hydride and δ-hydride,however their mechanisms for precipitation are still unclear.In the present study,we find that both γ-hydride and δ-hydride phases with different specific orientations were randomly precipitated in the as-received hot forged commercially pure Ti.In addition,a large amount of the titanium hydrides can be introduced into Ti matrix with selective precipitation by using electrochemical treatment.Cs-corrected scanning transmission electron microscopy is used to study the precipitation mechanisms of the two hydrides.It is revealed that the γ-hydride and δ-hydride precipitations are both formed through slip+shuffle mechanisms involving a unit of two layers of titanium atoms,but the difference is that the γ-hydride is formed by prismatic slip corresponding to hydrogen occupying the octahedral sites of α-Ti,while the δ-hydride is formed by basal slip corresponding to hydrogen occupying the tetrahedral sites ofα-Ti.展开更多
Surface enhanced Raman scattering(SERS)is a rapid and nondestructive technique that is capable of detecting and identifying chemical or biological compounds.Sensitive SERS quantification is vital for practical applica...Surface enhanced Raman scattering(SERS)is a rapid and nondestructive technique that is capable of detecting and identifying chemical or biological compounds.Sensitive SERS quantification is vital for practical applications,particularly for portable detection of biomolecules such as amino acids and nucleotides.However,few approaches can achieve sensitive and quantitative Raman detection of these most fundamental components in biology.Herein,a noblemetal-free single-atom site on a chip strategy was applied to modify single tungsten atom oxide on a lead halide perovskite,which provides sensitive SERS quantification for various analytes,including rhodamine,tyrosine and cytosine.The single-atom site on a chip can enable quantitative linear SERS responses of rhodamine(10^(−6)-1 mmol L^(−1)),tyrosine(0.06-1 mmol L^(−1))and cytosine(0.2-45 mmol L^(−1)),respectively,which all achieve record-high enhancement factors among plasmonic-free semiconductors.The experimental test and theoretical simulation both reveal that the enhanced mechanism can be ascribed to the controllable single-atom site,which can not only trap photoinduced electrons from the perovskite substrate but also enhance the highly efficient and quantitative charge transfer to analytes.Furthermore,the label-free strategy of single-atom sites on a chip can be applied in a portable Raman platform to obtain a sensitivity similar to that on a benchtop instrument,which can be readily extended to various biomolecules for low-cost,widely demanded and more precise point-of-care testing or in-vitro detection.展开更多
Electrode interfacial degradations are the key challenges for high-performance rechargeable batteries,usually mitigated through surface modification/coating strategies.Herein,we report a novel mechanism to enhance the...Electrode interfacial degradations are the key challenges for high-performance rechargeable batteries,usually mitigated through surface modification/coating strategies.Herein,we report a novel mechanism to enhance the surface stability of P2 layered cathodes by introducing a high density of dopant-enriched precipitates.Based on microscopic analysis,we show that forming a high density of precipitates at the grain surface can effectively suppress surface cracking and corrosion,which not only improves the surface/interface stability but also effectively suppresses the intergranular cracking issue.Increasing the doping level can lead to a greater density of precipitates at the surface region,which results in higher surface stability and increased cycling stability of the P2 layered cathode for a sodium-ion battery.We further reveal that prolonged cycling can induce the formation of a precipitate-free surface region due to the loss of Zn dopant and Na.Our in-depth microanalysis reveals cycling-induced dynamic structural evolution of the P2 layered cathodes,highlighting that dopant segregation-induced precipitation is a new approach to achieving high interfacial stability.展开更多
Comprehensive Summary Layered transition-metal oxides are promising cathode candidates for sodium-ion batteries.However,the inferior interphase formation and particulate fracture during sodiation/desodiation result in...Comprehensive Summary Layered transition-metal oxides are promising cathode candidates for sodium-ion batteries.However,the inferior interphase formation and particulate fracture during sodiation/desodiation result in structure degradation and poor stability.Herein,the interface chemistry of P2-Na_(0.640)Ni_(0.343)Mn_(0.657)O_(2)in an electrolyte of 1.0 mol/L NaPF6 in diglyme is unveiled to enable highly reversible Na extraction and intercalation.The uniform and robust cathode-electrolyte interphase layer is in situ formed with decomposition of diglyme molecules and anions in initial cycles.The NaF-and CO-rich CEI film exhibits high mechanical strength and ionic conductivity,which suppresses the reconstruction of its electrode interphase from P2 phase to spinel-like structure and reinforces its structure integrity without cracks.This favours facile Na+transport and stable bulk redox reactions.It is demonstrated to show long cycling stability with capacity retention of 94.4%for 180 cycles and superior rate capability.This investigation highlights the cathode interphase chemistry in sodium-ion batteries.展开更多
Clean energy innovation has triggered the development of single-atom catalysts(SACs)due to their excellent catalytic activity,high tunability and low cost.The success of SACs for many catalytic reactions has opened a ...Clean energy innovation has triggered the development of single-atom catalysts(SACs)due to their excellent catalytic activity,high tunability and low cost.The success of SACs for many catalytic reactions has opened a new field,where the fundamentals of catalytic property-structure relationship at atomic level await exploration,and thus raises challenges for structural characterization.Among the characterization techniques for SACs,aberration-corrected transmission electron microscopy(TEM)has become an essential tool for direct visualization of single atoms.In this review,we briefly summarize recent studies on SACs using advanced TEM.We first introduce TEM methods,which are particularly important for SACs characterization,and then discuss the applications of advanced TEM for SAC characterization,where not only atomic dispersion of single atoms can be studied,but also the distribution of elements and the valence state with local coordination can be resolved.We further extend our review towards in-situ TEM,which has increasing importance for the fundamental understanding of catalytic mechanism.Perspectives of TEM for SACs are finally discussed.展开更多
2 H phase molybdenum disulfide(2 H-MoS_(2))possesses the two-dimensional layered structure and high theoretical capacity,presenting excellent lithiation-delithiation property.However,the violent capacity decay within ...2 H phase molybdenum disulfide(2 H-MoS_(2))possesses the two-dimensional layered structure and high theoretical capacity,presenting excellent lithiation-delithiation property.However,the violent capacity decay within dozens of cycles still remains a great challenge due to lacking of in-depth failure mechanism.Herein,a novel decay-recovery-decay failure phenomenon upon long-term cycles is reported for the first time,which originates from the slow size change of Mo nanoparticles(NPs).Decay stages are triggered by many irregular-shaped Mo NPs with the increasing size up to~15 nm,leading to prominent pseudocapacitance failure and capacity loss.Subsequent recovery stages are attributed to the pulverization of coarse Mo NPs through surface sulfurization and accompanying lithiation.To overcome the instability issue,proper modifiers should be introduced to restrain the spontaneous growth of Mo NPs,such as aluminum oxide(Al_(2)O_(3)).The strong Mo-Al_(2)O_(3)bond gradually"drags"Al_(2)O_(3)fragments into the active material as the cycle continuously proceeds,resulting in the efficient refinement and the reversible conversion between Mo and MoS_(2).Therefore,the enhanced cycling stability and the capacity retention are successfully achieved.It is expected to provide a new insight into the energy storage of transition metal chalcogenide anode materials in rechargeable batteries.展开更多
基金supported by the National Natural Science Foundation of China (U21A2075, 22179117)the Fujian Science & Technology Innovation Laboratory for Energy Devices of China (21CLAB) (21C-OP-202107)the Program of Zhejiang University and Program of State Key Laboratory of Clean Energy Utilization at Zhejiang (ZJUCEU2020005)
文摘Solid-state polymer electrolytes(SPEs)have attracted increasing attention due to good interfacial contact,light weight,and easy manufacturing.However,the practical application of SPEs such as the most widely studied poly(ethylene oxide)(PEO)in high-energy solid polymer batteries is still challenging,and the reasons are yet elusive.Here,it is found that the mismatch between PEO and 4.2 V-class cathodes is beyond the limited electrochemical window of PEO in the solid Li Ni_(1/3)Mn_(1/3)Co_(1/3)O_(2)(NMC)-PEO batteries.The initial oxidation of PEO initiates remarkable surface reconstruction of NMC grains in solid batteries that are different from the situation in liquid electrolytes.Well-aligned nanovoids are observed in NMC grains during the diffusion of surface reconstruction layers towards the bulk in solid batteries.The substantial interphasial degradation,therefore,blocks smooth Li+transport across the NMC-PEO interface and causes performance degradation.A thin yet effective Li F-containing protection layer on NMC can effectively stabilize the NMC-PEO interface with a greatly improved lifespan of NMC|PEO|Li batteries.This work deepens the understanding of degradations in high-voltage solid-state polymer batteries.
基金supported by the National Key R&D Program of China(Nos.2020YFF0218200,2016YFB0300800 and 2021YFC1910505)the Innovation Fund Project of GRINM and other related projects.
文摘In addition to the three well-known Ag-related precipitates(Ω,X′and Z)in the Al-Cu-Mg-Ag alloys,Ag can also be involved in the formation of the as-cast second phases.However,the effect of Ag ad-dition in Al-Cu-Mg-Ag alloys has not been completely studied and even the structure of the as-cast Ag-containing phases is still controversial.By employing the focused ion beam(FIB)combined with transmis-sion electron microscopy(TEM)techniques and density functional theory(DFT)calculations,the forma-tion mechanisms of the Ag-containing phases in the as-cast Al-Cu-Mg-Ag alloys have been investigated.The Ag-containing phases are a series of hexagonal C14-type Laves phases with continuously varying Ag concentrations,described as(Al_(x)Cuy Ag_(1-x-y))_(2)Mg.Moreover,the specific occupancy sites of the atoms in(Al_(x)Cuy Ag_(1-x-y))_(2)Mg were determined.The formation of the(Al_(x)Cuy Ag_(1-x-y))_(2)Mg can be attributed to the stronger Ag-induced aggregation of solute atoms in the initial stage and the establishment of strong Ag-X(X=Al,Mg and Ag)bonding in the Ag-containing phases.Furthermore,our experiments have revealed the solidification sequence of Al-Cu-Mg-Ag alloys,and pointed out that(Al_(x)Cuy Ag_(1-x-y))_(2)Mg is formed at a lower temperature(493.9℃)through the reaction L■Al_(2)CuMg+(Al_(x)Cuy Ag_(1-x-y))_(2)Mg.The study could have positive implications for refinement of the Al-Cu-Mg-Ag quaternary phase diagram and promote the composition-property design of novel aluminum alloys based on(Al_(x)Cuy Ag_(1-x-y))_(2)Mg in the future.
基金the National Natural Science Foundation of China(U21A20172,21975028)the China Postdoctoral Science Foundation under Grant Number 2023 M740167.
文摘Enhancing the lifetime of perovskite solar cells(PSCs)is one of the essential challenges for their industrialization.Although the external encapsulation protects the perovskite device from the erosion of moisture and oxygen under various harsh conditions.However,the perovskite devices still undergo static and dynamic thermal stress during thermal and thermal cycling aging,respectively,resulting in irreversible damage to the morphology,component,and phase of stacked materials.Herein,the viscoelastic polymer polyvinyl butyral(PVB)material is designed onto the surface of perovskite films to form flexible interface encapsulation.After PVB interface encapsulation,the surface modulus of perovskite films decreases by nearly 50%,and the interface stress range under the dynamic temperature field(−40 to 85°C)drops from−42.5 to 64.8 MPa to−14.8 to 5.0 MPa.Besides,PVB forms chemical interactions with FA+cations and Pb^(2+),and the macroscopic residual stress is regulated and defects are reduced of the PVB encapsulated perovskite film.As a result,the optimized device's efficiency increases from 22.21%to 23.11%.Additionally,after 1500 h of thermal treatment(85°C),1000 h of damp heat test(85°C&85%RH),and 250 cycles of thermal cycling test(−40 to 85°C),the devices maintain 92.6%,85.8%,and 96.1%of their initial efficiencies,respectively.
基金supported by the National Key Research and Development Program of China (Grant Nos. 2017YFA0402802,2017YFA0206700)the National Natural Science Foundation of China (Grant Nos. 21776265, 51902304, and 52072358)+2 种基金the Natural Science Foundation of Anhui Province (Grant No.1908085ME122)the Fundamental Research Funds for the Central Universities (Grant No. Wk2060140026)the Hefei National Laboratory for Physical Sciences at the Microscale (Grant No.KF2020106)。
文摘Metal organic frameworks(MOFs) have been extensively investigated in Li-S batteries owing to high surface area, adjustable structures and abundant catalytic sites. Nevertheless, the insulating nature of traditional MOFs render retarded kinetics of polysulfides conversion, leading to insufficient utilization of sulfur. In comparison, conductive MOFs(c-MOFs) show great potential for promoting polysulfides transformation due to superb electronic conductivity. In this work, a nickel-catecholates based c-MOF, NiHHTP(HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene), is designed to regulate surface chemistry of self-supported carbon paper for advanced Li-S batteries. Taking advantage of the porous structure and high conductivity, the as-prepared Ni-HHTP is conducive to synergising strengthening the chemisorption of polysulfides and accelerating the reaction kinetics in Li-S batteries, significantly mitigating the polysulfides diffusion from the non-encapsulated sulfur cathode, therefore promoting polysulfides transformation in Li-S batteries. This work points out a promising modification strategy for developing advanced sulfur cathode in Li-S batteries.
基金supported by the National Key Research and Development Program of China(Nos.2017YFA0206700 and 2017YFA0402802)the National Natural Science Foundation of China(Nos.21776265 and 51902304)Anhui Provincial Natural Science Foundation(No.1908085ME122).
文摘Nitriles as efficient electrolyte additives are widely used in high-voltage lithium-ion batteries.However,their working mechanisms are still mysterious,especially in practical high-voltage LiCoO_(2)pouch lithium-ion batteries.Herein,we adopt a tridentate ligandcontaining 1,3,6-hexanetricarbonitrile(HTCN)as an effective electrolyte additive to shed light on the mechanism of stabilizing high-voltage LiCoO_(2)cathode(4.5 V)through nitriles.The LiCoO_(2)/graphite pouch cells with the HTCN additive electrolyte possess superior cycling performance,90%retention of the initial capacity after 800 cycles at 25℃,and 72%retention after 500 cycles at 45℃,which is feasible for practical application.Such an excellent cycling performance can be attributed to the stable interface:The HTCN molecules with strong electron-donating ability participate in the construction of cathode-electrolyte interphase(CEI)through coordinating with Co ions,which suppresses the decomposition of electrolyte and improves the structural stability of LiCoO_(2)during cycling.In summary,the work recognizes a coordinating-based interphase-forming mechanism as an effective strategy to optimize the performance of high voltage LiCoO_(2)cathode with appropriate electrolyte additives for practical pouch batteries.
基金supported financially by the National Natural Science Foundation of China (Nos. 11374028, U1330112 and 51621003)the National Natural Science Fund for Innovative Research Groups (No. 51621003)the Scientific Research Key Program of Beijing Municipal Commission of Education (No. KZ201310005002)
文摘■ compression twins with high density stacking faults were studied at atomic scale using Cscorrection transmission electron microscopy. On one side of the ■ twin boundary, there were many steps arranged alternately with the coherent twin boundaries. Most of the steps were linked with stacking faults inside twins. Burgers vector of twinning dislocations and the mismatch strain at steps were characterized. Due to the compressive mismatch strain at steps, the high density stacking faults inside twins were formed at twin tips during twinning process. The localized strain at the steps would be related to the crack nucleation in magnesium alloys.
基金This work was supported financially by the National Natural Science Foundation of China(Nos.51621003,11374028and U1330112)the Scientific Research Key Program of Beijing Municipal Commission of Education(No.KZ201310005002)+1 种基金the Beijing Municipal Found for Scientific Innovation(No.PXM2019014204500031)the Foundation on the Creative Research Team Construction Promotion Project of Beijing Municipal Institution(No.IDHT20190503)。
文摘Since titanium has high affinity for hydrogen and reacts reversibly with hydrogen,the precipitation of titanium hydrides in titanium and its alloys cannot be ignored.Two most common hydride precipitates in α-Ti matrix areγ-hydride and δ-hydride,however their mechanisms for precipitation are still unclear.In the present study,we find that both γ-hydride and δ-hydride phases with different specific orientations were randomly precipitated in the as-received hot forged commercially pure Ti.In addition,a large amount of the titanium hydrides can be introduced into Ti matrix with selective precipitation by using electrochemical treatment.Cs-corrected scanning transmission electron microscopy is used to study the precipitation mechanisms of the two hydrides.It is revealed that the γ-hydride and δ-hydride precipitations are both formed through slip+shuffle mechanisms involving a unit of two layers of titanium atoms,but the difference is that the γ-hydride is formed by prismatic slip corresponding to hydrogen occupying the octahedral sites of α-Ti,while the δ-hydride is formed by basal slip corresponding to hydrogen occupying the tetrahedral sites ofα-Ti.
基金supported by the Natural Science Foundation of Beijing Municipality(Z180014)。
文摘Surface enhanced Raman scattering(SERS)is a rapid and nondestructive technique that is capable of detecting and identifying chemical or biological compounds.Sensitive SERS quantification is vital for practical applications,particularly for portable detection of biomolecules such as amino acids and nucleotides.However,few approaches can achieve sensitive and quantitative Raman detection of these most fundamental components in biology.Herein,a noblemetal-free single-atom site on a chip strategy was applied to modify single tungsten atom oxide on a lead halide perovskite,which provides sensitive SERS quantification for various analytes,including rhodamine,tyrosine and cytosine.The single-atom site on a chip can enable quantitative linear SERS responses of rhodamine(10^(−6)-1 mmol L^(−1)),tyrosine(0.06-1 mmol L^(−1))and cytosine(0.2-45 mmol L^(−1)),respectively,which all achieve record-high enhancement factors among plasmonic-free semiconductors.The experimental test and theoretical simulation both reveal that the enhanced mechanism can be ascribed to the controllable single-atom site,which can not only trap photoinduced electrons from the perovskite substrate but also enhance the highly efficient and quantitative charge transfer to analytes.Furthermore,the label-free strategy of single-atom sites on a chip can be applied in a portable Raman platform to obtain a sensitivity similar to that on a benchtop instrument,which can be readily extended to various biomolecules for low-cost,widely demanded and more precise point-of-care testing or in-vitro detection.
基金P.Y.thank the National Natural Science Foundation of China(No.12174015)the Natural Science Foundation of Beijing,China(No.2212003)+4 种基金M.S.thank Innovative Research Group Project of the National Natural Science Foundation of China(grant no.51621003)Beijing Municipal High Level Innovative Team Building Program(IDHT20190503)K.W.thanks National Natural Science Foundation of China(No.12104024)China Postdoctoral Science Foundation(2020M680273)China National Postdoctoral Program for Innova-tive Talents(BX2021024).
文摘Electrode interfacial degradations are the key challenges for high-performance rechargeable batteries,usually mitigated through surface modification/coating strategies.Herein,we report a novel mechanism to enhance the surface stability of P2 layered cathodes by introducing a high density of dopant-enriched precipitates.Based on microscopic analysis,we show that forming a high density of precipitates at the grain surface can effectively suppress surface cracking and corrosion,which not only improves the surface/interface stability but also effectively suppresses the intergranular cracking issue.Increasing the doping level can lead to a greater density of precipitates at the surface region,which results in higher surface stability and increased cycling stability of the P2 layered cathode for a sodium-ion battery.We further reveal that prolonged cycling can induce the formation of a precipitate-free surface region due to the loss of Zn dopant and Na.Our in-depth microanalysis reveals cycling-induced dynamic structural evolution of the P2 layered cathodes,highlighting that dopant segregation-induced precipitation is a new approach to achieving high interfacial stability.
基金the National Natural Science Foundation of China(52171215)Haihe Laboratory of Sustainable Chemical Transformations,and China National Postdoctoral Program for Innovative Talents(BX2021024)。
文摘Comprehensive Summary Layered transition-metal oxides are promising cathode candidates for sodium-ion batteries.However,the inferior interphase formation and particulate fracture during sodiation/desodiation result in structure degradation and poor stability.Herein,the interface chemistry of P2-Na_(0.640)Ni_(0.343)Mn_(0.657)O_(2)in an electrolyte of 1.0 mol/L NaPF6 in diglyme is unveiled to enable highly reversible Na extraction and intercalation.The uniform and robust cathode-electrolyte interphase layer is in situ formed with decomposition of diglyme molecules and anions in initial cycles.The NaF-and CO-rich CEI film exhibits high mechanical strength and ionic conductivity,which suppresses the reconstruction of its electrode interphase from P2 phase to spinel-like structure and reinforces its structure integrity without cracks.This favours facile Na+transport and stable bulk redox reactions.It is demonstrated to show long cycling stability with capacity retention of 94.4%for 180 cycles and superior rate capability.This investigation highlights the cathode interphase chemistry in sodium-ion batteries.
基金National Natural Science Foundation of China(No.12074017)Beijing Municipal High Level Innovative Team Building Program,China(No.IDHT20190503)National Natural Science Fund for Innovative Research Groups of China(No.51621003).
文摘Clean energy innovation has triggered the development of single-atom catalysts(SACs)due to their excellent catalytic activity,high tunability and low cost.The success of SACs for many catalytic reactions has opened a new field,where the fundamentals of catalytic property-structure relationship at atomic level await exploration,and thus raises challenges for structural characterization.Among the characterization techniques for SACs,aberration-corrected transmission electron microscopy(TEM)has become an essential tool for direct visualization of single atoms.In this review,we briefly summarize recent studies on SACs using advanced TEM.We first introduce TEM methods,which are particularly important for SACs characterization,and then discuss the applications of advanced TEM for SAC characterization,where not only atomic dispersion of single atoms can be studied,but also the distribution of elements and the valence state with local coordination can be resolved.We further extend our review towards in-situ TEM,which has increasing importance for the fundamental understanding of catalytic mechanism.Perspectives of TEM for SACs are finally discussed.
基金financially supported by Beijing Municipal Great Wall Scholar Training Plan Project(CIT&TCD20190307)Beijing Municipal Commission of Education(KZ202210005003)+2 种基金National Natural Science Foundation of China(51621003,U1607110,12074017)Beijing Hundred,Thousand and Ten Thousand Talent Project(2020016)Beijing municipal high-level innovative team building program(IDHT20190503)。
文摘2 H phase molybdenum disulfide(2 H-MoS_(2))possesses the two-dimensional layered structure and high theoretical capacity,presenting excellent lithiation-delithiation property.However,the violent capacity decay within dozens of cycles still remains a great challenge due to lacking of in-depth failure mechanism.Herein,a novel decay-recovery-decay failure phenomenon upon long-term cycles is reported for the first time,which originates from the slow size change of Mo nanoparticles(NPs).Decay stages are triggered by many irregular-shaped Mo NPs with the increasing size up to~15 nm,leading to prominent pseudocapacitance failure and capacity loss.Subsequent recovery stages are attributed to the pulverization of coarse Mo NPs through surface sulfurization and accompanying lithiation.To overcome the instability issue,proper modifiers should be introduced to restrain the spontaneous growth of Mo NPs,such as aluminum oxide(Al_(2)O_(3)).The strong Mo-Al_(2)O_(3)bond gradually"drags"Al_(2)O_(3)fragments into the active material as the cycle continuously proceeds,resulting in the efficient refinement and the reversible conversion between Mo and MoS_(2).Therefore,the enhanced cycling stability and the capacity retention are successfully achieved.It is expected to provide a new insight into the energy storage of transition metal chalcogenide anode materials in rechargeable batteries.
