2,6-bis(picrylamino)-3,5-dinitropyridine(PYX)has excellent thermostability,which makes its thermal decomposition mechanism receive much attention.In this paper,the mechanism of PYX thermal decomposition was investigat...2,6-bis(picrylamino)-3,5-dinitropyridine(PYX)has excellent thermostability,which makes its thermal decomposition mechanism receive much attention.In this paper,the mechanism of PYX thermal decomposition was investigated thoroughly by the ReaxFF-lg force field combined with DFT-B3LYP(6-311++G)method.The detailed decomposition mechanism,small-molecule product evolution,and cluster evolution of PYX were mainly analyzed.In the initial stage of decomposition,the intramolecular hydrogen transfer reaction and the formation of dimerized clusters are earlier than the denitration reaction.With the progress of the reaction,one side of the bitter amino group is removed from the pyridine ring,and then the pyridine ring is cleaved.The final products produced in the thermal decomposition process are CO_(2),H_(2)O,N_(2),and H_(2).Among them,H_(2)O has the earliest generation time,and the reaction rate constant(k_(3))is the largest.Many clusters are formed during the decomposition of PYX,and the formation,aggregation,and decomposition of these clusters are strongly affected by temperature.At low temperatures(2500 K-2750 K),many clusters are formed.At high temperatures(2750 K-3250 K),the clusters aggregate to form larger clusters.At 3500 K,the large clusters decompose and become small.In the late stage of the reaction,H and N in the clusters escaped almost entirely,but more O was trapped in the clusters,which affected the auto-oxidation process of PYX.PYX's initial decomposition activation energy(E_(a))was calculated to be 126.58 kJ/mol.This work contributes to a theoretical understanding of PYX's entire thermal decomposition process.展开更多
Searching anodes with excellent electrochemical performance has been in great demand for rechargeable metal ion batteries. In this contribution, Fe/Co co-doped Ni S with N-based carbon(Fe Co-NiS@NC) derived from trime...Searching anodes with excellent electrochemical performance has been in great demand for rechargeable metal ion batteries. In this contribution, Fe/Co co-doped Ni S with N-based carbon(Fe Co-NiS@NC) derived from trimetallic Prussian blue analogue is designed and synthesized. The composition can be easily adjusted and modulated by multi-metals. In addition, the well-designed carbon nanocubes effectively promote electronic conductivity and buffer the volume change upon charge and discharge cycling, resulting in good capacity and long-term cycle life for both lithium-ion batteries and sodium-ion batteries, with capacities of 1018 m Ah g^(-1)(vs. Li/Li^(+)) and 454 m Ah g^(-1)(vs. Na/Na^(+)), respectively, after 100 cycles.Kinetics studies indicate that the electrochemical behaviors are manipulated by both diffusion and pseudocapacitance processes. These strategies would open new opportunities and potention for novel energy storage.展开更多
Rare-earth sulfides are of research interest for lithium-ion batteries(LIBs)due to their abundant lithium intercalation sites and low redox voltage.However,their electrochemical performances are not satisfactory becau...Rare-earth sulfides are of research interest for lithium-ion batteries(LIBs)due to their abundant lithium intercalation sites and low redox voltage.However,their electrochemical performances are not satisfactory because of poor conductivity and volume change upon electrochemical cycling.Herein,nanoarchitectures ofγ-Ce_(2)S_(3)encapsulated in a hollow mesoporous carbon nanosphere(Ce_(2)S_(3)@HMCS)are fabricated using the self-template strategy combined with the in-sphere sulfuration method and tested as an LIB anode.The void space between the Ce_(2)S_(3)core and the outer layer of the carbon nanosphere has been properly designed and modulated to achieve excellent electrochemical performance in terms of electronic conductivity,reversibility,and rate capability.The reversible capacity of Ce_(2)S_(3)@HMCS is 2.6 times that of the pure Ce_(2)S_(3)anode,which can gradually increase and maintain a capacity of 282 mAh·g^(−1)at a current density of 1 A·g^(-1),and a high Coulombic efficiency(~100%)can be achieved even after 1000 cycles.This good performance is attributed to the unique yolk-shell nanostructure with a highly crystallized and stable Ce3S2 core and volume expansion buffer space upon lithiation/delithiation.Ex situ X-ray diffraction and nuclear magnetic resonance results indicate that the lithiation of Ce_(2)S_(3)@HMCS is an intercalation process.This study represents an important advancement in precise structural design with in-sphere sulfuration and sheds light on a potential direction for highperformance lithium storage.展开更多
The effects of 14 factors on food production in Huang-Huai-Hai Plain are analyzed by path analysis in this paper,and then the linear regression models of them are established by SPSS software. The results show that el...The effects of 14 factors on food production in Huang-Huai-Hai Plain are analyzed by path analysis in this paper,and then the linear regression models of them are established by SPSS software. The results show that electricity consumption for agriculture,growing area of crops,the affected area,annual average temperature and arable land area at the end of the year have great effects on food production. Finally some recommendations are put forward to improve the food production in Huang-Huai-Hai Plain such as improving the level of agricultural mechanization,stabilizing food production,preventing natural disasters and increasing the effective irrigation area.展开更多
Lanthanum lithium titanate is one of the promising electrolytes for solid-state lithium-ion batteries due to its high bulk ionic conductivity up to∼10^(−3) S/cm.However,the practical application of this material has ...Lanthanum lithium titanate is one of the promising electrolytes for solid-state lithium-ion batteries due to its high bulk ionic conductivity up to∼10^(−3) S/cm.However,the practical application of this material has been bottlenecked by high grain boundary(GB)resistance,while the underlying mechanism is still under debate.Here we report a comprehensive study with direct evidence to reveal the origin of high GB resistance in La_(2/3)–xLi_(3x)TiO_(3)(LLTO).Atomic-scale observations via advanced scanning transmission electron microscopy show that the GBs are uniformly subject to subsurface segregation of La atoms to compensate for the excess surface charges.The La segregation leads to an abrupt decrease of charge carrier concentration neighboring GBs and hence is supposed to have deleterious effect on GB conductivity.The findings suggest a novel mechanism of space-charge-induced cation segregation,which shed lights on the intrinsic origin of low GB ionic conductivity in LLTO.展开更多
Anode SnO_(2)in lithium-ion batteries suffers from volume expansion and agglomeration.Here,the SnO_(2)nanoparticles are hybrided with ZrO_(2)particles by the support of carbon nanotube networks.The obtained SnO_(2)/C/...Anode SnO_(2)in lithium-ion batteries suffers from volume expansion and agglomeration.Here,the SnO_(2)nanoparticles are hybrided with ZrO_(2)particles by the support of carbon nanotube networks.The obtained SnO_(2)/C/ZrO_(2)composite shows improved electrochemical performances.Investigations reveal that the carbon nanotubes shorten the transmission path of electrons and Li^(+) ions.Ball milling with ZrO_(2)promotes the formation of nanosized SnO_(2)to weaken the internal strain change,being beneficial to buffering volume change during electrochemical cycling afterwards.High-resolution 6.7Li NMR investigations indicate that conversion and alloying reactions are stepwise involved for SnO_(2)/C/ZrO_(2)anode.The strategy of designing SnO_(2)/C/ZrO_(2)composite from the morphology-controlled metal-organic frameworks for energy storage widens the possibility to fabricate promising materials with enhanced performances.展开更多
基金funded by the National Natural Science Foundation of China(Grant No.21975024)。
文摘2,6-bis(picrylamino)-3,5-dinitropyridine(PYX)has excellent thermostability,which makes its thermal decomposition mechanism receive much attention.In this paper,the mechanism of PYX thermal decomposition was investigated thoroughly by the ReaxFF-lg force field combined with DFT-B3LYP(6-311++G)method.The detailed decomposition mechanism,small-molecule product evolution,and cluster evolution of PYX were mainly analyzed.In the initial stage of decomposition,the intramolecular hydrogen transfer reaction and the formation of dimerized clusters are earlier than the denitration reaction.With the progress of the reaction,one side of the bitter amino group is removed from the pyridine ring,and then the pyridine ring is cleaved.The final products produced in the thermal decomposition process are CO_(2),H_(2)O,N_(2),and H_(2).Among them,H_(2)O has the earliest generation time,and the reaction rate constant(k_(3))is the largest.Many clusters are formed during the decomposition of PYX,and the formation,aggregation,and decomposition of these clusters are strongly affected by temperature.At low temperatures(2500 K-2750 K),many clusters are formed.At high temperatures(2750 K-3250 K),the clusters aggregate to form larger clusters.At 3500 K,the large clusters decompose and become small.In the late stage of the reaction,H and N in the clusters escaped almost entirely,but more O was trapped in the clusters,which affected the auto-oxidation process of PYX.PYX's initial decomposition activation energy(E_(a))was calculated to be 126.58 kJ/mol.This work contributes to a theoretical understanding of PYX's entire thermal decomposition process.
基金supported by the National Natural Science Foundation of China(Grant Nos.21974007 and 22090043)。
文摘Searching anodes with excellent electrochemical performance has been in great demand for rechargeable metal ion batteries. In this contribution, Fe/Co co-doped Ni S with N-based carbon(Fe Co-NiS@NC) derived from trimetallic Prussian blue analogue is designed and synthesized. The composition can be easily adjusted and modulated by multi-metals. In addition, the well-designed carbon nanocubes effectively promote electronic conductivity and buffer the volume change upon charge and discharge cycling, resulting in good capacity and long-term cycle life for both lithium-ion batteries and sodium-ion batteries, with capacities of 1018 m Ah g^(-1)(vs. Li/Li^(+)) and 454 m Ah g^(-1)(vs. Na/Na^(+)), respectively, after 100 cycles.Kinetics studies indicate that the electrochemical behaviors are manipulated by both diffusion and pseudocapacitance processes. These strategies would open new opportunities and potention for novel energy storage.
基金National Natural Science Foundation of China,Grant/Award Numbers:21974007,U1930401 and U1530402。
文摘Rare-earth sulfides are of research interest for lithium-ion batteries(LIBs)due to their abundant lithium intercalation sites and low redox voltage.However,their electrochemical performances are not satisfactory because of poor conductivity and volume change upon electrochemical cycling.Herein,nanoarchitectures ofγ-Ce_(2)S_(3)encapsulated in a hollow mesoporous carbon nanosphere(Ce_(2)S_(3)@HMCS)are fabricated using the self-template strategy combined with the in-sphere sulfuration method and tested as an LIB anode.The void space between the Ce_(2)S_(3)core and the outer layer of the carbon nanosphere has been properly designed and modulated to achieve excellent electrochemical performance in terms of electronic conductivity,reversibility,and rate capability.The reversible capacity of Ce_(2)S_(3)@HMCS is 2.6 times that of the pure Ce_(2)S_(3)anode,which can gradually increase and maintain a capacity of 282 mAh·g^(−1)at a current density of 1 A·g^(-1),and a high Coulombic efficiency(~100%)can be achieved even after 1000 cycles.This good performance is attributed to the unique yolk-shell nanostructure with a highly crystallized and stable Ce3S2 core and volume expansion buffer space upon lithiation/delithiation.Ex situ X-ray diffraction and nuclear magnetic resonance results indicate that the lithiation of Ce_(2)S_(3)@HMCS is an intercalation process.This study represents an important advancement in precise structural design with in-sphere sulfuration and sheds light on a potential direction for highperformance lithium storage.
基金Supported by Soft Science Project of Shandong Province(2009RKB01052)
文摘The effects of 14 factors on food production in Huang-Huai-Hai Plain are analyzed by path analysis in this paper,and then the linear regression models of them are established by SPSS software. The results show that electricity consumption for agriculture,growing area of crops,the affected area,annual average temperature and arable land area at the end of the year have great effects on food production. Finally some recommendations are put forward to improve the food production in Huang-Huai-Hai Plain such as improving the level of agricultural mechanization,stabilizing food production,preventing natural disasters and increasing the effective irrigation area.
基金This work was supported by the National Natural Science Foundation of China(U2030206,22075003).
文摘Lanthanum lithium titanate is one of the promising electrolytes for solid-state lithium-ion batteries due to its high bulk ionic conductivity up to∼10^(−3) S/cm.However,the practical application of this material has been bottlenecked by high grain boundary(GB)resistance,while the underlying mechanism is still under debate.Here we report a comprehensive study with direct evidence to reveal the origin of high GB resistance in La_(2/3)–xLi_(3x)TiO_(3)(LLTO).Atomic-scale observations via advanced scanning transmission electron microscopy show that the GBs are uniformly subject to subsurface segregation of La atoms to compensate for the excess surface charges.The La segregation leads to an abrupt decrease of charge carrier concentration neighboring GBs and hence is supposed to have deleterious effect on GB conductivity.The findings suggest a novel mechanism of space-charge-induced cation segregation,which shed lights on the intrinsic origin of low GB ionic conductivity in LLTO.
基金support from the National Natural Science Foundation of China(Nos.21974007 and 22090043).
文摘Anode SnO_(2)in lithium-ion batteries suffers from volume expansion and agglomeration.Here,the SnO_(2)nanoparticles are hybrided with ZrO_(2)particles by the support of carbon nanotube networks.The obtained SnO_(2)/C/ZrO_(2)composite shows improved electrochemical performances.Investigations reveal that the carbon nanotubes shorten the transmission path of electrons and Li^(+) ions.Ball milling with ZrO_(2)promotes the formation of nanosized SnO_(2)to weaken the internal strain change,being beneficial to buffering volume change during electrochemical cycling afterwards.High-resolution 6.7Li NMR investigations indicate that conversion and alloying reactions are stepwise involved for SnO_(2)/C/ZrO_(2)anode.The strategy of designing SnO_(2)/C/ZrO_(2)composite from the morphology-controlled metal-organic frameworks for energy storage widens the possibility to fabricate promising materials with enhanced performances.
