Defect engineering acts as an efficiency method to modulate the microstructure and electronic structure of cathode for rechargeable magnesium batteries(RMBs).Owing to rich sulfur(S)vacancies tunes the electronic struc...Defect engineering acts as an efficiency method to modulate the microstructure and electronic structure of cathode for rechargeable magnesium batteries(RMBs).Owing to rich sulfur(S)vacancies tunes the electronic structure of VS4 with rich S vacancies(V_(S)-VS_(4)),the lower oxidation state of V^(3+)is induced for achieving the V^(3+)/V^(4+)and V^(4+)/V^(5+)multi-electrons reaction for Mg^(2+)storage.Amorphous structure is also constructed in VS-VS4 by chemical vapor deposition(CVD)method under the high temperature for providing fast magnesium ions(Mg^(2+))diffusion channels and expanding inner stress release space to balance the structural stability of multi-electrons reaction process.The simple defect engineering realizes the stable multi-electrons reaction in V_(S)-VS_(4) for enhancing its Mg^(2+)storage performance with higher specific capacity(158.6 mAh·g^(-1) at 50 mA·g^(-1)),stable cycling performance(capacity retention ratio of 72.7% after 3600 cycles)and the superior rate capability.This work provides electrode designing guidance for achieving stable multi-electrons to fully utilize the bivalent property of multivalence metal batteries.展开更多
Since the electrochemical energy storage was invented, mobile has brought us a new world without wires for more electronic devices [1–4]. Aluminum ion batteries(AIBs) were born with the requirements of electrochemica...Since the electrochemical energy storage was invented, mobile has brought us a new world without wires for more electronic devices [1–4]. Aluminum ion batteries(AIBs) were born with the requirements of electrochemical energy storage towards high capacity, safe and low cost.展开更多
Our previous work on the classical over-barrier ionization model for helium double ionization is extended to the complex multi-electron system of Ne. The total and q-fold ionization cross sections are calculated at en...Our previous work on the classical over-barrier ionization model for helium double ionization is extended to the complex multi-electron system of Ne. The total and q-fold ionization cross sections are calculated at energies ranging from a few tens to several hundred keV/u. The calculation results are in good agreement with the experimental data, and the energy dependence of the cross sections suggests that the multi-ionization of a strong perturbated complex atom is probably the sequential over-barrier ionization process.展开更多
Using the fully propagated time-dependent Hartree–Fock method, we identify that both the dynamic core polarization and multiorbital contributions are important in the attosecond transient absorption of CO molecules.T...Using the fully propagated time-dependent Hartree–Fock method, we identify that both the dynamic core polarization and multiorbital contributions are important in the attosecond transient absorption of CO molecules.The dynamics of core electrons effectively modifies the behaviors of electrons in the highest occupied molecular orbital, resulting in the modulation of intensity and position of the absorption peaks. Depending on the alignment angles, different inner orbitals are identified to contribute, and even dominate the total absorption spectra. As a result, multi-electron fingerprints are encoded in the absorption spectra, which shed light on future applications of attosecond transient absorption in complex systems.展开更多
Electrochemical batteries define the contraption stores electricity in the direct form of chemical energy with high efficiency. If the energy conversion process can be reversed, namely the input and output of electric...Electrochemical batteries define the contraption stores electricity in the direct form of chemical energy with high efficiency. If the energy conversion process can be reversed, namely the input and output of electricity both being permitted, the batteries are termed rechargeable batteries or also secondary batteries accordingly [1]. These decades have witnessed the rapid development of batteries because of the demands for transportation of information and mass in the mobile area, and stationary storage for the implementation of renewable energy technologies.展开更多
Rechargeable magnesium batteries(RMBs)hold promise for offering higher volumetric energy density and safety features,attracting increasing research interest as the next post lithium-ion batteries.Developing high perfo...Rechargeable magnesium batteries(RMBs)hold promise for offering higher volumetric energy density and safety features,attracting increasing research interest as the next post lithium-ion batteries.Developing high performance cathode material by inducing multi-electron reaction process as well as maintaining structural stability is the key to the development and application of RMBs.Herein,multielectron reaction occurred in VS_(4)by simple W doping strategy.W doping induces valence of partial V as V^(2+)and V^(3+)in VS_(4)structure,and then stimulates electrochemical reaction involving multi-electrons in 0.5%W-V-S.The flower-like microsphere morphology as well as rich S vacancies is also modulated by W doping to neutralize structure change in such multi-electron reaction process.The fabricated 0.5%W-V-S delivers higher specific capacity(149.3 m A h g^(-1)at 50 m A g^(-1),which is 1.6 times higher than that of VS_(4)),superior rate capability(76 mA h g^(-1)at 1000 mA g^(-1)),and stable cycling performance(1500cycles with capacity retention ratio of 93.8%).Besides that,pesudocapaticance-like contribution analysis as well as galvanostatic intermittent titration technique(GITT)further confirms the enhanced Mg^(2+)storage kinetics during such multi-electron involved electrochemical reaction process.Such discovery provides new insights into the designing of multi-electron reaction process in cathode as well as neutralizing structural change during such reaction for realizing superior electrochemical performance in energy storage devices.展开更多
The oxidative polymerization of aryl sulfoxides provides a novel polysulfo-nium compound, poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene cation) in quantita-tive yield. The polymerization proceeds efficiently in ...The oxidative polymerization of aryl sulfoxides provides a novel polysulfo-nium compound, poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene cation) in quantita-tive yield. The polymerization proceeds efficiently in an acidic solution under atmosphericconditions. Oxygen, chemical and electrochemical oxidations are available. Vanadyl acety-lacetonate and cerium ammonium nitrate act as an effective catalyst for the oxygen ox-idative polymerization. The polymerization mechanism involves multielectron oxidation ofthe sulfides followed by successive electrophilic substitution. The resulting polyarylenesul-fonium cations are useful as a soluble precursor for the synthesis of high molecular weight(M_w>10~5) poly(thio arylne)s.展开更多
Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into...Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO_(2) are not clear. Hence, based on the first-principles calculations, key influencing factors of slow Al-ions diffusion are narrow pathways, unstable Al-O bonds and Mn^(3+) type polaron have been identified by investigating four types of δ-MnO_(2)(O3, O'3, P2 and T1). Although Al insert into δ-MnO_(2) leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO_(2) keeps the long(spacious pathways)and stable(2.007–2.030 A) Al-O bonds resulting in the lower energy barrier of Al diffusion of 0.56 e V. By eliminated the influence of Mn^(3+)(low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 e V in P2 type, confirming the obviously effect of Mn^(3+) polaron. On the contrary, although the T1 type MnO_(2) has the sluggish of Al-ions diffusion, the larger interlayer spacing of Mn-Mn layer,causing by H_(2)O could assist Al-ions diffusion. Furthermore, it is worth to notice that the multilayer δ-MnO_(2) achieves multi-electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2(1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO_(2) should keep more P2-type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage.展开更多
Influence of core property on multi-electron process in the collisions of q = 6-9 and 11 isocharged sequence ions with Ne is investigated in the keV/u region. The cross-section ratios of double-, triple-, quadruple- a...Influence of core property on multi-electron process in the collisions of q = 6-9 and 11 isocharged sequence ions with Ne is investigated in the keV/u region. The cross-section ratios of double-, triple-, quadruple- and total multielectron processes to the single electron capture process as well as the partial ratios of different reaction channels to the relevant multi-electron process are measured by using position-sensitive and time-of-flight techniques. The experimental data are compared with the theoretical predictions including the extended classical over-barrier model, the molecular Columbic barrier model and the semi-empirical scaling law. Results show a core effect on multi-electron process of isocharge ions colliding with Neon, which is consistent with the results of Helium we obtained previously.展开更多
We derive a new differential formula about a kind of product of polynomials and then apply it to analyze some properties of multi-electron state ＂related to Laughlin wave function＂. The entangled state representatio...We derive a new differential formula about a kind of product of polynomials and then apply it to analyze some properties of multi-electron state ＂related to Laughlin wave function＂. The entangled state representation for describing electrons in uniform magnetic field is used.展开更多
Sodium superionic conductors(NASICONs)have attracted enormous attention owing to their excellent ionic diffusion and structural stability.However,the high cost of vanadium,limited capacity due to fewer redox reactions...Sodium superionic conductors(NASICONs)have attracted enormous attention owing to their excellent ionic diffusion and structural stability.However,the high cost of vanadium,limited capacity due to fewer redox reactions,and low electronic conductivity restrict their practical application.Herein,we designed Na_(3.5)V_(0.5)Mn_(0.5)Fe_(0.5)Ti_(0.5)(PO_(4))3 (NVMFTP)medium entropy NASICON with multi-electron reactions as a fast sodium storage cathode for sodium-ion batteries(SIBs).The incorporation of Fe,Mn and Ti not only reduces the cost but also activates multi-redox reactions of V^(2+)/V^(3+),Ti^(3+)/Ti^(4+),Fe^(2+)/Fe^(3+),V^(3+)/V^(4+),Mn^(2+)/Mn^(3+),V^(4+)/V^(5+).Owing to distinctive structural design with medium entropy,the NVMFTP delivered 168 mAh·g^(−1) at 0.5C with a remarkable rate capability of 93.51 mAh·g^(−1) at 60C and steady long-term cycling performance till 5000 cycles.More importantly,NVMFTP takes only 11 min to achieve 80%SOC at 5C.The in-situ and ex-situ X-ray diffraction(XRD)further demonstrate reversible multi-electron reaction mechanisms of slow charging and fast charging.NVMFTP/HC full cell shows 110 mAh·g^(−1) capacity and 208 Wh·kg^(−1) energy density.This study will provide comprehensive insight into developing low-cost,cutting-edge materials for SIBs.展开更多
The accurate theoretical expressions of the mean field operator associated with the multi-configuration time-dependent Hartree-Fock （MCTDHF） method are presented in this paper. By using a theoretical formula, derive...The accurate theoretical expressions of the mean field operator associated with the multi-configuration time-dependent Hartree-Fock （MCTDHF） method are presented in this paper. By using a theoretical formula, derived without approxima- tion, we can study the multi-electron correlation dynamics accurately. Some illustrative calculations are carried out to check the accuracy of the expression of the mean field operator. The results of illustrative calculations indicate the reliability of the accurate expression of the mean field operator. This theoretical calculation method for the mean field operator may be of considerable help in future studies of the correlated dynamics of many-electron systems in strong laser fields.展开更多
Magnesium rechargeable batteries(MRBs)present opportunities for grid-scale energy storage applications as a complement to Li-ion batteries(LIBS).The major challenges are the low reversible capacity,inferior cycling st...Magnesium rechargeable batteries(MRBs)present opportunities for grid-scale energy storage applications as a complement to Li-ion batteries(LIBS).The major challenges are the low reversible capacity,inferior cycling stability and unsatisfactory energy densities.Na_(3)VCr_(0.5)Fe_(0.5)(PO_(4))_(3) with a well-defined NASIONtype structure is used as cathode in Mg cell.Two-electrons reaction(~116 m Ah/g),1.5 V average voltage and 65%of capacity retention over 100 cycles are accomplished.Mg is inserted by a biphasic reaction with the participation of V3+/V4+/V5+redox couples in the electrochemical reaction while the non-active redox couples such as Cr^(3+)/Cr^(4+)and Fe^(2+)/Fe^(3+)served as stabilizer to buffer the volume variation.A thermal stability up to~412℃ is also exhibited.Therefore,incorporating a mixture of three transition metal(V/Cr/Fe)in this type of structures will broaden new perspectives for realizing high performance cathodes for MRBs.展开更多
To address increasing energy supply challenges and allow for the effective utilization of renewable energy sources,transformational and reliable battery chemistry are critically needed to obtain higher energy densitie...To address increasing energy supply challenges and allow for the effective utilization of renewable energy sources,transformational and reliable battery chemistry are critically needed to obtain higher energy densities.Here,significant progress has been made in the past few decades in energetic battery systems based on the concept of multi-electron reactions to overcome existing barriers in conventional battery research and application.As a result,a systematic understanding of multi-electron chemistry is essential for the design of novel multi-electron reaction materials and the enhancement of corresponding battery performances.Based on this,this review will briefly present the advancements of multi-electron reaction materials from their evolutionary discovery from lightweight elements to the more recent multi-ion effect.In addition,this review will discuss representative multi-electron reaction chemistry and materials,including ferrates,metal borides,metal oxides,metal fluorides,lithium transition metal oxides,silicon,sulfur and oxygen.Furthermore,insertion-type,alloy-type and conversion-type multi-electron chemistry involving monovalent Li^(+) and Na^(+) cations,polyvalent Mg^(2+) and Al^(3+) cations beyond those of alkali metals as well as activated S^(2−) and O^(2−) anions are introduced in the enrichment and development of multi-electron reactions for electrochemical energy storage applications.Finally,this review will present the ongoing challenges and underpinning mechanisms limiting the performance of multi-electron reaction materials and corresponding battery systems.展开更多
The growing concern about scarcity and large-scale applications of lithium resources has attracted efforts to realize cost-effective phosphate-based cathode materials for next-generation Na-ion batteries(NIBs).In prev...The growing concern about scarcity and large-scale applications of lithium resources has attracted efforts to realize cost-effective phosphate-based cathode materials for next-generation Na-ion batteries(NIBs).In previous work,a series of materials(such as Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7)),Na_(3)VCr(PO_(4))_(3),Na_(4)VMn(PO_(4))3,Na_(3)MnTi(PO_(4))_(3),Na_(3)MnZr(PO_(4))3,etc)with∼120 mAh g^(-1) specific capacity and high operating potential has been proposed.However,the mass ratio of the total transition metal in the above compounds is only∼22 wt%,which means that one-electron transfer for each transition metal shows a limited capacity(the mass ratio of Fe is 35.4 wt%in LiFePO_(4)).Therefore,a multi-electron transfer reaction is necessary to catch up to or go beyond the electrochemical performance of LiFePO_(4).This review summarizes the reported NASICON-type and other phosphate-based cathode materials.On the basis of the aforementioned experimental results,we pinpoint the multi-electron behavior of transition metals and shed light on designing rules for developing high-capacity cathodes in NIBs.展开更多
Aqueous zinc-ion batteries(AZIBs)have attracted increasing interest due to their intrinsic safety and low cost,yet their energy density remains limited by the lack of suitable cathode materials.Covalent organic framew...Aqueous zinc-ion batteries(AZIBs)have attracted increasing interest due to their intrinsic safety and low cost,yet their energy density remains limited by the lack of suitable cathode materials.Covalent organic frameworks(COFs),with tunable porosity,structural diversity,and redox-site designability,have emerged as promising AZIBs cathodes.The integration of multiple redox-active sites,such as carbonyl(C=O)and imine(C=N)groups,enables stepwise multi-electron transfer,offering a pathway to higher capacity and voltage output.This review systematically categorizes COFs into n-type,p-type,and bipolar systems based on redox-active moieties and analyzes their charge storage behaviors through cyclic voltammetry(CV).We focus on how the spatial arrangement and electronic nature of C=O/C=N sites influence one-,two-,or three-step electron transfer,as well as Zn2+and H+co-insertion mechanisms.Electrochemical performances,redox kinetics,molecular structure,and electrolyte adaptability are also discussed in detail.By elucidating the structure-mechanism relationships of redox-active COFs,this review highlights molecular design principles that enhance redox-site utilization and energy density.The insights provided herein aim to guide the development of next-generation,high-performance organic cathodes for multi-electron AZIBs.展开更多
Metal organic frameworks have been employed as high-performance layered double hydroxide(LDH)composite supercapacitor electrode materials but have shown unsatisfactory redox ability and stability.Herein,a host-vip C...Metal organic frameworks have been employed as high-performance layered double hydroxide(LDH)composite supercapacitor electrode materials but have shown unsatisfactory redox ability and stability.Herein,a host-vip CuMo-based polyoxomet-alate-based metal organic framework(POMOF)with copious electrochemically active sites and strong electrochemical redox activi-ties has been effectively coupled with POM-incorporated CoNi-LDH to develop a nanocomposite(NENU-5@CoNi-LDH)by a simple solvothermal method.The designed electrode shows a high specific capacity of 333.61 mAh·g^(-1) at 1 A·g^(-1).In addition,the novel hy-brid symmetric supercapacitor NENU-5@CoNi-LDH/active carbon(AC)demonstrated a high energy density of 80.8 Wh·kg^(-1) at a power density of 750.7 W·kg^(-1).Interestingly,the nanocomposite of NENU-5@CoNi-LDH exhibits an outstanding capacitance reten-tion of 79%after 5000 charge-discharge cycles at 10 A·g^(-1).This work provides a new strategy and will be the backbone for future energy storage research.展开更多
By use of optical spectrum technology, the spectra of X-ray induced by highly charged 40Arq+ ions interacting with Au surface have been studied. The results show that the argon Kα X-ray were emitted from the hollow a...By use of optical spectrum technology, the spectra of X-ray induced by highly charged 40Arq+ ions interacting with Au surface have been studied. The results show that the argon Kα X-ray were emitted from the hollow atoms formed below the surface. There is a process of multi-electron exciting in neutralization of the Ar16+ion, with electronic con-figuration 1s2 in its ground state below the solid surface. The yield of the projectile Kα X-ray is related to its initial electronic configuration, and the yield of the target X-ray is related to the projectile kinetic energy.展开更多
Sodium superionic conductors(NASICONs)show significant promise for application in the development of cathodes for sodium-ion batteries(SIBs).However,it remains a major challenge to develop the desired multi-electron r...Sodium superionic conductors(NASICONs)show significant promise for application in the development of cathodes for sodium-ion batteries(SIBs).However,it remains a major challenge to develop the desired multi-electron reaction cathode with a high specific capacity and energy density.Herein,we report a novel NASICON-type Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)cathode obtained by combining electrospinning and stepwise sintering processes.This cathode exhibits a high discharge capacity of 160.4 mAh g^(−1)and operates at a considerable medium voltage of 3.2 V.The Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)cathode undergoes a multi-electron redox reaction involving the Cr^(3+/4+)(4.40/4.31 V vs.Na/Na^(+)),Mn^(3+/4+)(4.18/4.03 V),Mn^(2+/3+)(3.74/3.41 V),and Ti^(3+/4+)(2.04/2.14 V)redox couples.This redox reaction enables a three-electron transfer during the Na+intercalation/de-intercalation processes.As a result,the Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)demonstrates a significant enhancement in energy density,surpassing other recently reported SIB cathodes.The highly reversible structure evolution and small volume changes during cycling were demonstrated with in-situ X-ray diffraction,ensuring outstanding cyclability with 77%capacity retention after 500 cycles.Furthermore,a NMCTP@C//Sb@C full battery was fabricated,which delivered a high energy density of 421 Wh kg−1 and exhibited good cyclability with 75.7%capacity retention after 100 cycles.The rational design of composition regulation with multi-metal ion substitution holds the potential to unlock new possibilities in achieving high-performance SIBs.展开更多
The X-ray spectra of Nb surface induced by Arq+ (q =16,17) ions with the energy range from 10 to 20 keV/q were studied by the optical spectrum technology. The experimental results indicate that the multi-electron exci...The X-ray spectra of Nb surface induced by Arq+ (q =16,17) ions with the energy range from 10 to 20 keV/q were studied by the optical spectrum technology. The experimental results indicate that the multi-electron excitation occurred as a highly charged Ar16+ ion was neutralized below the metal surface. The K shell electron of Ar16+ was excited and then de-excited cascadly to emit K X-ray. The intensity of the X-ray emitted from K shell of the hollow Ar atom decreased with the increase of projectile kinetic energy. The intensity of the X-ray emitted from L shell of the target atom Nb increased with the increase of projectile kinetic energy. The X-ray yield of Ar17+ is three magnitude orders larger than that of Ar16+.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52072196,52002200,52102106,52202262,22379081,and 22379080)Major Basic Research Program of Natural Science Foundation of Shandong Province(No.ZR2020ZD09)+1 种基金the Natural Science Foundation of Shandong Province(Nos.ZR2020QE063,ZR202108180009,and ZR2023QE059)the Postdoctoral Program of Qingdao(No.QDBSH20220202019).
文摘Defect engineering acts as an efficiency method to modulate the microstructure and electronic structure of cathode for rechargeable magnesium batteries(RMBs).Owing to rich sulfur(S)vacancies tunes the electronic structure of VS4 with rich S vacancies(V_(S)-VS_(4)),the lower oxidation state of V^(3+)is induced for achieving the V^(3+)/V^(4+)and V^(4+)/V^(5+)multi-electrons reaction for Mg^(2+)storage.Amorphous structure is also constructed in VS-VS4 by chemical vapor deposition(CVD)method under the high temperature for providing fast magnesium ions(Mg^(2+))diffusion channels and expanding inner stress release space to balance the structural stability of multi-electrons reaction process.The simple defect engineering realizes the stable multi-electrons reaction in V_(S)-VS_(4) for enhancing its Mg^(2+)storage performance with higher specific capacity(158.6 mAh·g^(-1) at 50 mA·g^(-1)),stable cycling performance(capacity retention ratio of 72.7% after 3600 cycles)and the superior rate capability.This work provides electrode designing guidance for achieving stable multi-electrons to fully utilize the bivalent property of multivalence metal batteries.
基金supported by the National Natural Science Foundation of China (Grant No. 22075028)。
文摘Since the electrochemical energy storage was invented, mobile has brought us a new world without wires for more electronic devices [1–4]. Aluminum ion batteries(AIBs) were born with the requirements of electrochemical energy storage towards high capacity, safe and low cost.
基金Project supported the by the National Natural Science Foundation of China (Grant No. 10804039)the Fundamental Research Funds for the Central Universities,China (Grant No. lzujbky-2009-24)
文摘Our previous work on the classical over-barrier ionization model for helium double ionization is extended to the complex multi-electron system of Ne. The total and q-fold ionization cross sections are calculated at energies ranging from a few tens to several hundred keV/u. The calculation results are in good agreement with the experimental data, and the energy dependence of the cross sections suggests that the multi-ionization of a strong perturbated complex atom is probably the sequential over-barrier ionization process.
基金Supported by the National Basic Research Program of China under Grant No 2013CB922203the National Natural Science Foundation of China under Grant No 11374366+1 种基金the Innovation Foundation of National University of Defense Technology under Grant No B110204the Hunan Provincial Innovation Foundation for Postgraduate under Grant No CX2011B010
文摘Using the fully propagated time-dependent Hartree–Fock method, we identify that both the dynamic core polarization and multiorbital contributions are important in the attosecond transient absorption of CO molecules.The dynamics of core electrons effectively modifies the behaviors of electrons in the highest occupied molecular orbital, resulting in the modulation of intensity and position of the absorption peaks. Depending on the alignment angles, different inner orbitals are identified to contribute, and even dominate the total absorption spectra. As a result, multi-electron fingerprints are encoded in the absorption spectra, which shed light on future applications of attosecond transient absorption in complex systems.
基金the National Basic Research Program of China (Grant Nos. 2015CB251100, 2009CB220100, 2002CB211800) for financial support。
文摘Electrochemical batteries define the contraption stores electricity in the direct form of chemical energy with high efficiency. If the energy conversion process can be reversed, namely the input and output of electricity both being permitted, the batteries are termed rechargeable batteries or also secondary batteries accordingly [1]. These decades have witnessed the rapid development of batteries because of the demands for transportation of information and mass in the mobile area, and stationary storage for the implementation of renewable energy technologies.
基金supported by the National Natural Science Foundation of China under Grant No.52072196,52002200,52102106,52202262,22379081,and 22379080Major Basic Research Program of the Natural Science Foundation of Shandong Province under Grant No.ZR2020ZD09+1 种基金the Natural Science Foundation of Shandong Province under Grant No.ZR2020QE063,ZR202108180009,ZR2023QE059the Postdoctoral Program in Qingdao under No.QDBSH20220202019。
文摘Rechargeable magnesium batteries(RMBs)hold promise for offering higher volumetric energy density and safety features,attracting increasing research interest as the next post lithium-ion batteries.Developing high performance cathode material by inducing multi-electron reaction process as well as maintaining structural stability is the key to the development and application of RMBs.Herein,multielectron reaction occurred in VS_(4)by simple W doping strategy.W doping induces valence of partial V as V^(2+)and V^(3+)in VS_(4)structure,and then stimulates electrochemical reaction involving multi-electrons in 0.5%W-V-S.The flower-like microsphere morphology as well as rich S vacancies is also modulated by W doping to neutralize structure change in such multi-electron reaction process.The fabricated 0.5%W-V-S delivers higher specific capacity(149.3 m A h g^(-1)at 50 m A g^(-1),which is 1.6 times higher than that of VS_(4)),superior rate capability(76 mA h g^(-1)at 1000 mA g^(-1)),and stable cycling performance(1500cycles with capacity retention ratio of 93.8%).Besides that,pesudocapaticance-like contribution analysis as well as galvanostatic intermittent titration technique(GITT)further confirms the enhanced Mg^(2+)storage kinetics during such multi-electron involved electrochemical reaction process.Such discovery provides new insights into the designing of multi-electron reaction process in cathode as well as neutralizing structural change during such reaction for realizing superior electrochemical performance in energy storage devices.
基金This work was partially supported by a Grant-in-Aid for Research Fellow of the Japan Society for the Promotion of Science(No.085410)and International Scientific Research(Joint Research No.08044174)from the Ministry of Education,Science,Sports and Culture
文摘The oxidative polymerization of aryl sulfoxides provides a novel polysulfo-nium compound, poly(methylsulfonio-1,4-phenylenethio-1,4-phenylene cation) in quantita-tive yield. The polymerization proceeds efficiently in an acidic solution under atmosphericconditions. Oxygen, chemical and electrochemical oxidations are available. Vanadyl acety-lacetonate and cerium ammonium nitrate act as an effective catalyst for the oxygen ox-idative polymerization. The polymerization mechanism involves multielectron oxidation ofthe sulfides followed by successive electrophilic substitution. The resulting polyarylenesul-fonium cations are useful as a soluble precursor for the synthesis of high molecular weight(M_w>10~5) poly(thio arylne)s.
基金supported financially by the National Natural Science Foundation of China (No.22075028)。
文摘Rechargeable aluminum batteries with multi-electron reaction have a high theoretical capacity for next generation of energy storage devices. However, the diffusion mechanism and intrinsic property of Al insertion into MnO_(2) are not clear. Hence, based on the first-principles calculations, key influencing factors of slow Al-ions diffusion are narrow pathways, unstable Al-O bonds and Mn^(3+) type polaron have been identified by investigating four types of δ-MnO_(2)(O3, O'3, P2 and T1). Although Al insert into δ-MnO_(2) leads to a decrease in the spacing of the Mn-Mn layer, P2 type MnO_(2) keeps the long(spacious pathways)and stable(2.007–2.030 A) Al-O bonds resulting in the lower energy barrier of Al diffusion of 0.56 e V. By eliminated the influence of Mn^(3+)(low concentration of Al insertion), the energy barrier of Al migration achieves 0.19 e V in P2 type, confirming the obviously effect of Mn^(3+) polaron. On the contrary, although the T1 type MnO_(2) has the sluggish of Al-ions diffusion, the larger interlayer spacing of Mn-Mn layer,causing by H_(2)O could assist Al-ions diffusion. Furthermore, it is worth to notice that the multilayer δ-MnO_(2) achieves multi-electron reaction of 3|e|. Considering the requirement of high energy density, the average voltage of P2(1.76 V) is not an obstacle for application as cathode in RABs. These discover suggest that layered MnO_(2) should keep more P2-type structure in the synthesis of materials and increase the interlayer spacing of Mn-Mn layer for providing technical support of RABs in large-scale energy storage.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 10874188 and 10775160)
文摘Influence of core property on multi-electron process in the collisions of q = 6-9 and 11 isocharged sequence ions with Ne is investigated in the keV/u region. The cross-section ratios of double-, triple-, quadruple- and total multielectron processes to the single electron capture process as well as the partial ratios of different reaction channels to the relevant multi-electron process are measured by using position-sensitive and time-of-flight techniques. The experimental data are compared with the theoretical predictions including the extended classical over-barrier model, the molecular Columbic barrier model and the semi-empirical scaling law. Results show a core effect on multi-electron process of isocharge ions colliding with Neon, which is consistent with the results of Helium we obtained previously.
基金The project supported by National Natural Science Foundation of China under Grant No. 10475056
文摘We derive a new differential formula about a kind of product of polynomials and then apply it to analyze some properties of multi-electron state ＂related to Laughlin wave function＂. The entangled state representation for describing electrons in uniform magnetic field is used.
基金supported by the National Natural Science Foundation of China(Nos.52027801 and 92263203)the National Key R&D Program of China(Nos.2022YFA1203902 and 2022YFA1200093)and the China-Germany Collaboration Project(No.M-0199)。
文摘Sodium superionic conductors(NASICONs)have attracted enormous attention owing to their excellent ionic diffusion and structural stability.However,the high cost of vanadium,limited capacity due to fewer redox reactions,and low electronic conductivity restrict their practical application.Herein,we designed Na_(3.5)V_(0.5)Mn_(0.5)Fe_(0.5)Ti_(0.5)(PO_(4))3 (NVMFTP)medium entropy NASICON with multi-electron reactions as a fast sodium storage cathode for sodium-ion batteries(SIBs).The incorporation of Fe,Mn and Ti not only reduces the cost but also activates multi-redox reactions of V^(2+)/V^(3+),Ti^(3+)/Ti^(4+),Fe^(2+)/Fe^(3+),V^(3+)/V^(4+),Mn^(2+)/Mn^(3+),V^(4+)/V^(5+).Owing to distinctive structural design with medium entropy,the NVMFTP delivered 168 mAh·g^(−1) at 0.5C with a remarkable rate capability of 93.51 mAh·g^(−1) at 60C and steady long-term cycling performance till 5000 cycles.More importantly,NVMFTP takes only 11 min to achieve 80%SOC at 5C.The in-situ and ex-situ X-ray diffraction(XRD)further demonstrate reversible multi-electron reaction mechanisms of slow charging and fast charging.NVMFTP/HC full cell shows 110 mAh·g^(−1) capacity and 208 Wh·kg^(−1) energy density.This study will provide comprehensive insight into developing low-cost,cutting-edge materials for SIBs.
基金supported by the Scientific Research Program of the Higher Education Institution of Xinjiang, China (Grant No. XJEDU2012S41)the National Natural Science Foundation of China (Grant No. 10974198)
文摘The accurate theoretical expressions of the mean field operator associated with the multi-configuration time-dependent Hartree-Fock （MCTDHF） method are presented in this paper. By using a theoretical formula, derived without approxima- tion, we can study the multi-electron correlation dynamics accurately. Some illustrative calculations are carried out to check the accuracy of the expression of the mean field operator. The results of illustrative calculations indicate the reliability of the accurate expression of the mean field operator. This theoretical calculation method for the mean field operator may be of considerable help in future studies of the correlated dynamics of many-electron systems in strong laser fields.
基金supported by the Scientific Research Funds of Huaqiao University and Xiamen University Foreign Young Talents Program(No.G2022149004L)。
文摘Magnesium rechargeable batteries(MRBs)present opportunities for grid-scale energy storage applications as a complement to Li-ion batteries(LIBS).The major challenges are the low reversible capacity,inferior cycling stability and unsatisfactory energy densities.Na_(3)VCr_(0.5)Fe_(0.5)(PO_(4))_(3) with a well-defined NASIONtype structure is used as cathode in Mg cell.Two-electrons reaction(~116 m Ah/g),1.5 V average voltage and 65%of capacity retention over 100 cycles are accomplished.Mg is inserted by a biphasic reaction with the participation of V3+/V4+/V5+redox couples in the electrochemical reaction while the non-active redox couples such as Cr^(3+)/Cr^(4+)and Fe^(2+)/Fe^(3+)served as stabilizer to buffer the volume variation.A thermal stability up to~412℃ is also exhibited.Therefore,incorporating a mixture of three transition metal(V/Cr/Fe)in this type of structures will broaden new perspectives for realizing high performance cathodes for MRBs.
基金support from the National Basic Research Program of China(Grant Nos.2015CB251100,2009CB220100,2002CB211800)the National Natural Science Foundation of China(Grant Nos.21975026,51804290)+2 种基金the Beijing Natural Science Foundation(Grant Nos.L182023,L182056).G.Tan acknowledges the support from Beijing Institute of Technology Teli Young Fellow Program(No.3090011181903)X.Wang thanks the support from the Beijing Institute of Technology Research Fund Program for Young Scholars(2019CX04092).
文摘To address increasing energy supply challenges and allow for the effective utilization of renewable energy sources,transformational and reliable battery chemistry are critically needed to obtain higher energy densities.Here,significant progress has been made in the past few decades in energetic battery systems based on the concept of multi-electron reactions to overcome existing barriers in conventional battery research and application.As a result,a systematic understanding of multi-electron chemistry is essential for the design of novel multi-electron reaction materials and the enhancement of corresponding battery performances.Based on this,this review will briefly present the advancements of multi-electron reaction materials from their evolutionary discovery from lightweight elements to the more recent multi-ion effect.In addition,this review will discuss representative multi-electron reaction chemistry and materials,including ferrates,metal borides,metal oxides,metal fluorides,lithium transition metal oxides,silicon,sulfur and oxygen.Furthermore,insertion-type,alloy-type and conversion-type multi-electron chemistry involving monovalent Li^(+) and Na^(+) cations,polyvalent Mg^(2+) and Al^(3+) cations beyond those of alkali metals as well as activated S^(2−) and O^(2−) anions are introduced in the enrichment and development of multi-electron reactions for electrochemical energy storage applications.Finally,this review will present the ongoing challenges and underpinning mechanisms limiting the performance of multi-electron reaction materials and corresponding battery systems.
基金supported by the National Key R&D Program of China(2022YFB3807800)National Natural Science Foundation(NSFC)of China(51725206,52122214,52002394,and 52072403)Youth Innovation Promotion Association of the Chinese Academy of Sciences(2020006).
文摘The growing concern about scarcity and large-scale applications of lithium resources has attracted efforts to realize cost-effective phosphate-based cathode materials for next-generation Na-ion batteries(NIBs).In previous work,a series of materials(such as Na_(4)Fe_(3)(PO_(4))_(2)(P_(2)O_(7)),Na_(3)VCr(PO_(4))_(3),Na_(4)VMn(PO_(4))3,Na_(3)MnTi(PO_(4))_(3),Na_(3)MnZr(PO_(4))3,etc)with∼120 mAh g^(-1) specific capacity and high operating potential has been proposed.However,the mass ratio of the total transition metal in the above compounds is only∼22 wt%,which means that one-electron transfer for each transition metal shows a limited capacity(the mass ratio of Fe is 35.4 wt%in LiFePO_(4)).Therefore,a multi-electron transfer reaction is necessary to catch up to or go beyond the electrochemical performance of LiFePO_(4).This review summarizes the reported NASICON-type and other phosphate-based cathode materials.On the basis of the aforementioned experimental results,we pinpoint the multi-electron behavior of transition metals and shed light on designing rules for developing high-capacity cathodes in NIBs.
基金supported by the National Natural Science Foundation of China(No.52403221).
文摘Aqueous zinc-ion batteries(AZIBs)have attracted increasing interest due to their intrinsic safety and low cost,yet their energy density remains limited by the lack of suitable cathode materials.Covalent organic frameworks(COFs),with tunable porosity,structural diversity,and redox-site designability,have emerged as promising AZIBs cathodes.The integration of multiple redox-active sites,such as carbonyl(C=O)and imine(C=N)groups,enables stepwise multi-electron transfer,offering a pathway to higher capacity and voltage output.This review systematically categorizes COFs into n-type,p-type,and bipolar systems based on redox-active moieties and analyzes their charge storage behaviors through cyclic voltammetry(CV).We focus on how the spatial arrangement and electronic nature of C=O/C=N sites influence one-,two-,or three-step electron transfer,as well as Zn2+and H+co-insertion mechanisms.Electrochemical performances,redox kinetics,molecular structure,and electrolyte adaptability are also discussed in detail.By elucidating the structure-mechanism relationships of redox-active COFs,this review highlights molecular design principles that enhance redox-site utilization and energy density.The insights provided herein aim to guide the development of next-generation,high-performance organic cathodes for multi-electron AZIBs.
基金financially supported by the National Natural Science Foundation of China(22001156)the Youth Talent Fund of University Association for Science and Technology in Shaanxi,China(20210602)the Science Foundation of Science and Technology Department of Shaanxi Province(2021JQ-533).
文摘Metal organic frameworks have been employed as high-performance layered double hydroxide(LDH)composite supercapacitor electrode materials but have shown unsatisfactory redox ability and stability.Herein,a host-vip CuMo-based polyoxomet-alate-based metal organic framework(POMOF)with copious electrochemically active sites and strong electrochemical redox activi-ties has been effectively coupled with POM-incorporated CoNi-LDH to develop a nanocomposite(NENU-5@CoNi-LDH)by a simple solvothermal method.The designed electrode shows a high specific capacity of 333.61 mAh·g^(-1) at 1 A·g^(-1).In addition,the novel hy-brid symmetric supercapacitor NENU-5@CoNi-LDH/active carbon(AC)demonstrated a high energy density of 80.8 Wh·kg^(-1) at a power density of 750.7 W·kg^(-1).Interestingly,the nanocomposite of NENU-5@CoNi-LDH exhibits an outstanding capacitance reten-tion of 79%after 5000 charge-discharge cycles at 10 A·g^(-1).This work provides a new strategy and will be the backbone for future energy storage research.
基金the National Natural Science Foundation of China (Grant Nos.10274088,10405025 , 10574132 )the Special Program for Key Basic Research Projects of the Ministry of Science and Technology (Grant No. 2002CCA00900) the Education Commission Foundation of Shaanxi Province (Grant No.04JK300).
文摘By use of optical spectrum technology, the spectra of X-ray induced by highly charged 40Arq+ ions interacting with Au surface have been studied. The results show that the argon Kα X-ray were emitted from the hollow atoms formed below the surface. There is a process of multi-electron exciting in neutralization of the Ar16+ion, with electronic con-figuration 1s2 in its ground state below the solid surface. The yield of the projectile Kα X-ray is related to its initial electronic configuration, and the yield of the target X-ray is related to the projectile kinetic energy.
基金supported by the National Natural Science Foundation of China(52302304,52102299,52102295)the Guangdong Basic and Applied Basic Research Foundation(2021A1515110059)+3 种基金the Natural Science Foundation of Hubei Provincial(2023AFB999)the Fundamental Research Funds for the Central Universities(WUT:2021IVA034B,2022-xcs4)Hainan Provincial Joint Project of Sanya Yazhou Bay Science and Technology City(520LH055)the Sanya Science and Education Innovation Park of Wuhan University of Technology(2021KF0019).
文摘Sodium superionic conductors(NASICONs)show significant promise for application in the development of cathodes for sodium-ion batteries(SIBs).However,it remains a major challenge to develop the desired multi-electron reaction cathode with a high specific capacity and energy density.Herein,we report a novel NASICON-type Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)cathode obtained by combining electrospinning and stepwise sintering processes.This cathode exhibits a high discharge capacity of 160.4 mAh g^(−1)and operates at a considerable medium voltage of 3.2 V.The Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)cathode undergoes a multi-electron redox reaction involving the Cr^(3+/4+)(4.40/4.31 V vs.Na/Na^(+)),Mn^(3+/4+)(4.18/4.03 V),Mn^(2+/3+)(3.74/3.41 V),and Ti^(3+/4+)(2.04/2.14 V)redox couples.This redox reaction enables a three-electron transfer during the Na+intercalation/de-intercalation processes.As a result,the Na_(3.5)MnCr_(0.5)Ti_(0.5)(PO_(4))_(3)demonstrates a significant enhancement in energy density,surpassing other recently reported SIB cathodes.The highly reversible structure evolution and small volume changes during cycling were demonstrated with in-situ X-ray diffraction,ensuring outstanding cyclability with 77%capacity retention after 500 cycles.Furthermore,a NMCTP@C//Sb@C full battery was fabricated,which delivered a high energy density of 421 Wh kg−1 and exhibited good cyclability with 75.7%capacity retention after 100 cycles.The rational design of composition regulation with multi-metal ion substitution holds the potential to unlock new possibilities in achieving high-performance SIBs.
基金Supported by the National Natural Science Foundation of China (Grant Nos.10774149 and 10405025)
文摘The X-ray spectra of Nb surface induced by Arq+ (q =16,17) ions with the energy range from 10 to 20 keV/q were studied by the optical spectrum technology. The experimental results indicate that the multi-electron excitation occurred as a highly charged Ar16+ ion was neutralized below the metal surface. The K shell electron of Ar16+ was excited and then de-excited cascadly to emit K X-ray. The intensity of the X-ray emitted from K shell of the hollow Ar atom decreased with the increase of projectile kinetic energy. The intensity of the X-ray emitted from L shell of the target atom Nb increased with the increase of projectile kinetic energy. The X-ray yield of Ar17+ is three magnitude orders larger than that of Ar16+.
