P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phas...P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.展开更多
A comparative study of two kinds of oxidants(H2O and O3) with the combination of two metal precursors(TMA and La(~iPrCp)3) for atomic layer deposition(ALD) La2O3/Al2O3 nanolaminates is carried out. The effect...A comparative study of two kinds of oxidants(H2O and O3) with the combination of two metal precursors(TMA and La(~iPrCp)3) for atomic layer deposition(ALD) La2O3/Al2O3 nanolaminates is carried out. The effects of different oxidants on the physical properties and electrical characteristics of La2O3/Al2O3 nanolaminates are studied. Initial testing results indicate that La2O3/Al2O3 nanolaminates could avoid moisture absorption in the air after thermal annealing. However, moisture absorption occurs in H2O-based La2O3/Al2O3 nanolaminates due to the residue hydroxyl/hydrogen groups during annealing. As a result, roughness enhancement, band offset variation, low dielectric constant and poor electrical characteristics are measured because the properties of H2O-based La2O3/Al2O3 nanolaminates are deteriorated. Addition thermal annealing effects on the properties of O3-based La2O3/Al2O3 nanolaminates indicate that O3 is a more appropriate oxidant to deposit La2O3/Al2O3 nanolaminates for electron devices application.展开更多
The adsorption of C atoms on the α-Fe2O3(001) surface was studied based on density function theory(DFT) ,in which the exchange-correlation potential was chosen as the PBE(Perdew,Burke and Ernzerhof) generalized...The adsorption of C atoms on the α-Fe2O3(001) surface was studied based on density function theory(DFT) ,in which the exchange-correlation potential was chosen as the PBE(Perdew,Burke and Ernzerhof) generalized gradient approximation(GGA) with a plane wave basis set. Upon the optimization on different adsorption sites with coverage of 1/20 and 1/5 ML,it was found that the adsorption of C atoms on the α-Fe2O3(001) surface was chemical adsorption. The coverage can affect the adsorption behavior greatly. Under low coverage,the most stable adsorption geometry lied on the bridged site with the adsorption energy of about 3.22 eV; however,under high coverage,it located at the top site with the energy change of 8.79 eV. Strong chemical reaction has occurred between the C and O atoms at this site. The density of states and population analysis showed that the s,p orbitals of C and p orbital of O give the most contribution to the adsorption bonding. During the adsorption process,O atom shares the electrons with C,and C can only affect the outermost and subsurface layers of α-Fe2O3; the third layer can not be affected obviously.展开更多
Chemical and field-effect passivation of atomic layer deposition (ALD) Al2O3 films are investigated, mainly by corona charging measurement. The interface structure and material properties are characterized by transm...Chemical and field-effect passivation of atomic layer deposition (ALD) Al2O3 films are investigated, mainly by corona charging measurement. The interface structure and material properties are characterized by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), respectively. Passivation performance is improved remarkably by annealing at temperatures of 450 ℃ and 500 ℃, while the improvement is quite weak at 600 ℃, which can be attributed to the poor quality of chemical passivation. An increase of fixed negative charge density in the films during annealing can be explained by the Al2O3/Si interface structural change. The Al–OH groups play an important role in chemical passivation, and the Al–OH concentration in an as-deposited film subsequently determines the passivation quality of that film when it is annealed, to a certain degree.展开更多
Effects of initial surface termination on electrical characteristics of La2O3/Al2O3 nanolaminates deposited by atomic layer deposition are studied by conductive atomic force microscopy working in contact mode and stan...Effects of initial surface termination on electrical characteristics of La2O3/Al2O3 nanolaminates deposited by atomic layer deposition are studied by conductive atomic force microscopy working in contact mode and standard electrical characterization methods.It is found that,compared with La2O3/Al2O3 nanolaminates with LaOx as termination,lower interface trap density,less current leakage spots,and higher breakdown voltage are obtained in the La2O3/Al2O3 nanolaminates with AlOx as termination after annealing.A clear promotion of interface silicate layer is observed for La2O3/Al2O3 nanolaminates with AlOx as termination compared with LaOx as termination under the same annealing condition.In addition,the current conduction mechanism in La2O3/Al2O3 nanolaminates is considered as the Poole-Frenkel conduction.All results indicate that the AlOx is a more appropriate termination to deposit La2O3/Al2O3 nanolaminates on Si substrate,which is useful for the high-κ process development.展开更多
ion reaction of O (3P) with Si2H6 has been studied theoretically. Two transition states of 3A and 3A symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 level with ...ion reaction of O (3P) with Si2H6 has been studied theoretically. Two transition states of 3A and 3A symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 level with 6-311G+(d) basis set. G3MP2 has been used for the final single-point energy calculation. The rate constants have been calculated over a wide temperature range of 200~3000 K using canonical variational transition-state theory (CVT) with small curvature tunneling effect (SCT). The calculated CVT/SCT rate constants match well with the experimental value.展开更多
基金supported by the National Natural Science Foundation of China (22169002)the Chongzuo Key Research and Development Program of China (20220603)the Counterpart Aid Project for Discipline Construction from Guangxi University(2023M02)
文摘P2/O3-type Ni/Mn-based layered oxides are promising cathode materials for sodium-ion batteries(SIBs)owing to their high energy density.However,exploring effective ways to enhance the synergy between the P2 and 03 phases remains a necessity.Herein,we design a P2/O3-type Na_(0.76)Ni_(0.31)Zn_(0.07)Mn_(0.50)Ti_(0.12)0_(2)(NNZMT)with high chemical/electrochemical stability by enhancing the coupling between the two phases.For the first time,a unique Na*extraction is observed from a Na-rich O3 phase by a Na-poor P2 phase and systematically investigated.This process is facilitated by Zn^(2+)/Ti^(4+)dual doping and calcination condition regulation,allowing a higher Na*content in the P2 phase with larger Na^(+)transport channels and enhancing Na transport kinetics.Because of reduced Na^(+)in the O3 phase,which increases the difficulty of H^(+)/Na^(+) exchange,the hydrostability of the O3 phase in NNZMT is considerably improved.Furthermore,Zn^(2+)/Ti^(4+)presence in NNZMT synergistically regulates oxygen redox chemistry,which effectively suppresses O_(2)/CO_(2) gas release and electrolyte decomposition,and completely inhibits phase transitions above 4.0 V.As a result,NNZMT achieves a high discharge capacity of 144.8 mA h g^(-1) with a median voltage of 3.42 V at 20 mA g^(-1) and exhibits excellent cycling performance with a capacity retention of 77.3% for 1000 cycles at 2000 mA g^(-1).This study provides an effective strategy and new insights into the design of high-performance layered-oxide cathode materials with enhanced structure/interface stability forSIBs.
基金supported by the National Natural Science Foundation of China(Grant Nos.61604016 and 51501017)the Fundamental Research Funds for the Central Universities,China(Grant No.310831161003)
文摘A comparative study of two kinds of oxidants(H2O and O3) with the combination of two metal precursors(TMA and La(~iPrCp)3) for atomic layer deposition(ALD) La2O3/Al2O3 nanolaminates is carried out. The effects of different oxidants on the physical properties and electrical characteristics of La2O3/Al2O3 nanolaminates are studied. Initial testing results indicate that La2O3/Al2O3 nanolaminates could avoid moisture absorption in the air after thermal annealing. However, moisture absorption occurs in H2O-based La2O3/Al2O3 nanolaminates due to the residue hydroxyl/hydrogen groups during annealing. As a result, roughness enhancement, band offset variation, low dielectric constant and poor electrical characteristics are measured because the properties of H2O-based La2O3/Al2O3 nanolaminates are deteriorated. Addition thermal annealing effects on the properties of O3-based La2O3/Al2O3 nanolaminates indicate that O3 is a more appropriate oxidant to deposit La2O3/Al2O3 nanolaminates for electron devices application.
基金Project supported by the Foundation for Key Program of Ministry of Education (Nos.108033 and 107119)State Key Development Program for Basic Research of China (No.2009CB219801)+4 种基金the National High Technology Research and Development Program of China (No.2008AA05Z302)NNSFC (No.50976032)NSF of Beijing (No.3101001)the Specialized Basic Research Fund for Center Higher Education (No.09ZG03)Doctor Fund of North China Electric Power University (No.200822015)
文摘The adsorption of C atoms on the α-Fe2O3(001) surface was studied based on density function theory(DFT) ,in which the exchange-correlation potential was chosen as the PBE(Perdew,Burke and Ernzerhof) generalized gradient approximation(GGA) with a plane wave basis set. Upon the optimization on different adsorption sites with coverage of 1/20 and 1/5 ML,it was found that the adsorption of C atoms on the α-Fe2O3(001) surface was chemical adsorption. The coverage can affect the adsorption behavior greatly. Under low coverage,the most stable adsorption geometry lied on the bridged site with the adsorption energy of about 3.22 eV; however,under high coverage,it located at the top site with the energy change of 8.79 eV. Strong chemical reaction has occurred between the C and O atoms at this site. The density of states and population analysis showed that the s,p orbitals of C and p orbital of O give the most contribution to the adsorption bonding. During the adsorption process,O atom shares the electrons with C,and C can only affect the outermost and subsurface layers of α-Fe2O3; the third layer can not be affected obviously.
基金Project supported by the National Natural Science Foundation of China(Grant No.61106060)the Knowledge Innovation Program of the Chinese Academy of Sciences(Grant No.Y2YF028001)the National High Technology Research and Development Program of China(Grant No.2012AA052401)
文摘Chemical and field-effect passivation of atomic layer deposition (ALD) Al2O3 films are investigated, mainly by corona charging measurement. The interface structure and material properties are characterized by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS), respectively. Passivation performance is improved remarkably by annealing at temperatures of 450 ℃ and 500 ℃, while the improvement is quite weak at 600 ℃, which can be attributed to the poor quality of chemical passivation. An increase of fixed negative charge density in the films during annealing can be explained by the Al2O3/Si interface structural change. The Al–OH groups play an important role in chemical passivation, and the Al–OH concentration in an as-deposited film subsequently determines the passivation quality of that film when it is annealed, to a certain degree.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.61604016 and 51802025)China Postdoctoral Science Foundation(Grant No.2017M613028)+1 种基金the Fundamental Research Funds for the Central Universities,China(Grant Nos.300102319209 and 300102310501)the Innovation,and Entrepreneurship Training Program for Undergraduates(Grant Nos.202010710231 and 201910710564).
文摘Effects of initial surface termination on electrical characteristics of La2O3/Al2O3 nanolaminates deposited by atomic layer deposition are studied by conductive atomic force microscopy working in contact mode and standard electrical characterization methods.It is found that,compared with La2O3/Al2O3 nanolaminates with LaOx as termination,lower interface trap density,less current leakage spots,and higher breakdown voltage are obtained in the La2O3/Al2O3 nanolaminates with AlOx as termination after annealing.A clear promotion of interface silicate layer is observed for La2O3/Al2O3 nanolaminates with AlOx as termination compared with LaOx as termination under the same annealing condition.In addition,the current conduction mechanism in La2O3/Al2O3 nanolaminates is considered as the Poole-Frenkel conduction.All results indicate that the AlOx is a more appropriate termination to deposit La2O3/Al2O3 nanolaminates on Si substrate,which is useful for the high-κ process development.
基金The authors thank Professor Donald G. Truhlar for providing the POLYRATE 7.8 programThis work is supported by the Research Fund for the Doctoral Program of Higher Education of China.
文摘ion reaction of O (3P) with Si2H6 has been studied theoretically. Two transition states of 3A and 3A symmetries have been located for this abstraction reaction. Geometries have been optimized at the UMP2 level with 6-311G+(d) basis set. G3MP2 has been used for the final single-point energy calculation. The rate constants have been calculated over a wide temperature range of 200~3000 K using canonical variational transition-state theory (CVT) with small curvature tunneling effect (SCT). The calculated CVT/SCT rate constants match well with the experimental value.