Emulsification is one of the important mechanisms of surfactant flooding. To improve oil recovery for low permeability reservoirs, a highly efficient emulsification oil flooding system consisting of anionic surfactant...Emulsification is one of the important mechanisms of surfactant flooding. To improve oil recovery for low permeability reservoirs, a highly efficient emulsification oil flooding system consisting of anionic surfactant sodium alkyl glucosyl hydroxypropyl sulfonate(APGSHS) and zwitterionic surfactant octadecyl betaine(BS-18) is proposed. The performance of APGSHS/BS-18 mixed surfactant system was evaluated in terms of interfacial tension, emulsification capability, emulsion size and distribution, wettability alteration, temperature-resistance and salt-resistance. The emulsification speed was used to evaluate the emulsification ability of surfactant systems, and the results show that mixed surfactant systems can completely emulsify the crude oil into emulsions droplets even under low energy conditions. Meanwhile,the system exhibits good temperature and salt resistance. Finally, the best oil recovery of 25.45% is achieved for low permeability core by the mixed surfactant system with a total concentration of 0.3 wt%while the molar ratio of APGSHS:BS-18 is 4:6. The current study indicates that the anionic/zwitterionic mixed surfactant system can improve the oil flooding efficiency and is potential candidate for application in low permeability reservoirs.展开更多
Zwitterionic materials with covalently tethered cations and anions have great potential as electrolyte additives for aqueous Znion batteries(AZIBs)owing to their appealing intrinsic characteristics and merits.However,...Zwitterionic materials with covalently tethered cations and anions have great potential as electrolyte additives for aqueous Znion batteries(AZIBs)owing to their appealing intrinsic characteristics and merits.However,the impact of cationic and anionic moieties within zwitterions on enhancing the performance of AZIBs remains poorly understood.Herein,three zwitterions,namely carboxybetaine methacrylate(CBMA),sulfobetaine methacrylate(SBMA),and 2-methacryloyloxyethyl phosphorylcholine(MPC),were selected as additives to investigate their different action mechanisms in AZIBs.All three zwitterions have the same quaternary ammonium as the positively charged group,but having different negatively charged segments,i.e.,carboxylate,sulfonate,and phosphate for CBMA,SBMA,and MPC,respectively.By systematical electrochemical analysis,these zwitterions all contribute to enhanced cycling life of Zn anode,with MPC having the most pronounced effect,which can be attributed to the synergistic effect of positively quaternary ammonium group and unique negatively phosphate groups.As a result,the Zn//Zn cell with MPC as additive in ZnSO_(4)electrolyte exhibits an ultralong lifespan over 5000 h.This work proposes new insights to the future development of multifunctional zwitterionic additives for remarkably stable AZIBs.展开更多
Lysozyme,myoglobin and BSA were used as models of globular proteins covering a wide range of pl.The purpose is to extend the studies to anionic lipid bilayers.Electrostatics is studied in cationic protein adsorption t...Lysozyme,myoglobin and BSA were used as models of globular proteins covering a wide range of pl.The purpose is to extend the studies to anionic lipid bilayers.Electrostatics is studied in cationic protein adsorption to zwitterionic PC and anionic mixed PC/PG SUVs.Protein adsorption is investigated in SUVs along with changes of fluorescence emission spectra.Partition coefficients and cooperativity parameters are calculated.At pl binding obtains maximum while at lower or higher pHs binding decreases.In Gouy-Chapman formalism activity coefficient goes with square charge,which deviations indicate asymmetric location of anionic phospholipid in the inner leaflet,in mixed SUVs for lysozyme-and myoglobin-PC/PG systems,in agreement with experiments and molecular dynamics simulations.Vesicles bind myoglobin anti-cooperatively while lysozyme-BSA cooperativitivey.A model is proposed for both,which composes two protein sub-layers with different structures and properties.Hill coefficient reflects subunit cooperativity of bi and tridomain proteins.展开更多
Flexible strain sensors have received tremendous attention because of their potential applications as wearable sensing devices.However, the integration of key functions into a single sensor, such as high stretchabilit...Flexible strain sensors have received tremendous attention because of their potential applications as wearable sensing devices.However, the integration of key functions into a single sensor, such as high stretchability, low hysteresis, self-adhesion, andexcellent antifreezing performance, remains an unmet challenge. In this respect, zwitterionic hydrogels have emerged asideal material candidates for breaking through the above dilemma. The mechanical properties of most reported zwitterionichydrogels, however, are relatively poor, significantly restricting their use under load-bearing conditions. Traditional improve-ment approaches often involve complex preparation processes, making large-scale production challenging. Additionally,zwitterionic hydrogels prepared with chemical crosslinkers are typically fragile and prone to irreversible deformation underlarge strains, resulting in the slow recovery of structure and function. To fundamentally enhance the mechanical properties ofpure zwitterionic hydrogels, the most effective approach is the regulation of the chemical structure of zwitterionic monomersthrough a targeted design strategy. This study employed a novel zwitterionic monomer carboxybetaine urethane acrylate(CBUTA), which contained one urethane group and one carboxybetaine group on its side chain. Through the direct polym-erization of ultrahigh concentration monomer solutions without adding any chemical crosslinker, we successfully developedpure zwitterionic supramolecular hydrogels with significantly enhanced mechanical properties, self-adhesive behavior, andantifreezing performance. Most importantly, the resultant zwitterionic hydrogels exhibited high tensile strength and tough-ness and displayed ultralow hysteresis under strain conditions up to 1100%. This outstanding performance was attributedto the unique liquid–liquid phase separation phenomenon induced by the ultrahigh concentration of CBUTA monomers inan aqueous solution, as well as the enhanced polymer chain entanglement and the strong hydrogen bonds between urethanegroups on the side chains. The potential application of hydrogels in strain sensors and high-performance triboelectric nano-generators was further explored. Overall, this work provides a promising strategy for developing pure zwitterionic hydrogelsfor flexible strain sensors and self-powered electronic devices.展开更多
Traditional hydrogels are inevitably damaged during practical applications,resulting in a gradual deterioration of their functional efficacy.A primary strategy to address this issue involves developing hydrogels with ...Traditional hydrogels are inevitably damaged during practical applications,resulting in a gradual deterioration of their functional efficacy.A primary strategy to address this issue involves developing hydrogels with inherent self-healing properties.In this study,we report the synthesis of self-healing polyacrylate hydrogels that integrate zwitterions,hydrophilic nano-silica and aluminum ions.Due to the synergistic effect of multiple hydrogen bonds,coordination bonds and electrostatic interactions,the tensile strength of the hydrogel is enhanced from 15.1 to 162.6 kPa.Moreover,the electrical resistance and tensile strength of the hydrogel can almost recover to its initial values after 20 min of healing at room temperature,exhibiting remarkable self-healing performance.Furthermore,the zwitterionic polyacrylate hydrogel serves as a wearable sensor with the capability of accurately response to the bending and stretching of human joints,exhibting a gauge factor of 1.87 under tensile strain ranging from 80% to 100%.Even after being freezed at-20℃ for 3 h,the zwitterionic polyacrylate hydrogel retains its exceptional writing performance.In conclusion,the hydrogels developed in this study demonstrate significant potential for wearable electronics applications.展开更多
The objective of this study was to predict,screen,synthesize,and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid(PA).To improve t...The objective of this study was to predict,screen,synthesize,and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid(PA).To improve the efficiency and success rate of experimental screening,two virtual tools based on hydrogen bond propensity(HBP)and modified molecular electrostatic potential(MEP)maps were used.The prediction accuracy of HBP and MEP is 58.82%and 94.11%,respectively,presenting that the MEP model is very powerful in the discovery of pharmaceutical cocrystals.Among the 12 successfully obtained cocrystals,4 single crystals of PA with luteolin(LUT),genistein(GEN),taxifolin(TAX),dihydromyricetin(DHM)were obtained for the first time.Charged-assisted O-H…O and N-H…O hydrogen bonds appear as main hydrogen bonding synthons,and PA adopts a zwitterionic form after cocrystallization.GEN-PA,TAX-PA,and DHM-PA showed higher DPPH'radical-scavenging capacities;LUT-PA and DHM-PA showed higher ABTS^(+)radical-scavenging capacities;GEN-PA and DHM-PA possessed better protective effects on H9c2 cells from hypoxic injury caused by CoCl_(2)than corresponding pure flavonoids.展开更多
The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic...The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic frameworks formed by B–O and B–O–F units significantly determine the physical properties of fluorooxoborates.Therefore,the rational design of anionic frameworks could facilitate the materials discovery process.Herein,we propose that a candidate anionic framework can be efficiently derived from an existing one by slightly altering its oxygen content.Following this idea,we hypothesized the existence of a 1D[B_(3)O_(5)F]_(∞)chain from the wellknown 2D[B_(6)O_(9)F_(2_)]_(∞)layer.Accordingly,seven CaB_(3)O_(5)F structures with the expected anionic framework were successfully predicted.First-principles calculations show that all these structures have potential in the UV/DUV birefringent or nonlinear optical(NLO)material field,indicating that the 1D[B_(3)O_(5)F]_(∞)chain is indeed a promising anionic framework for achieving UV/DUV birefringent and NLO performance.展开更多
Electrides,characterized by spatially confined anionic electrons,have emerged as a promising class of materials for catalysis,magnetism,and superconductivity.However,transition-metal-based electrides with diverse elec...Electrides,characterized by spatially confined anionic electrons,have emerged as a promising class of materials for catalysis,magnetism,and superconductivity.However,transition-metal-based electrides with diverse electron dimensionalities remain largely unexplored.Here,we perform a comprehensive first-principles investigation of Y-Co electrides,focusing on Y_(3)Co,Y_(3)Co_(2),and YCo.Our calculations reveal a striking dimensional evolution of anionic electrons:from two-dimensional(2D)confinement in YCo to one-dimensional(1D)in Y_(3)Co_(2)and zero-dimensional(0D)in Y_(3)Co.Remarkably,the YCo monolayer exhibits intrinsic ferromagnetism,with a magnetic moment of 0.65μB per formula unit arising from spin-polarized anionic electrons mediating long-range coupling between Y and Co ions.The monolayer also shows a low exfoliation energy(1.66 J/m^(2)),indicating experimental feasibility.All three electrides exhibit low work functions(2.76 eV-3.11 eV)along with Co-centered anionic states.This work expands the family of transition-metal-based electrides and highlights dimensionality engineering as a powerful strategy for tuning electronic and magnetic properties.展开更多
As the global exploration and development of oil and gas resources advances into deep formations,the harsh conditions of high temperature and high salinity present significant challenges for drilling fluids.In order t...As the global exploration and development of oil and gas resources advances into deep formations,the harsh conditions of high temperature and high salinity present significant challenges for drilling fluids.In order to address the technical difficulties associated with the failure of filtrate loss reducers under high-temperature and high-salinity conditions.In this study,a hydrophobic zwitterionic filtrate loss reducer(PDA)was synthesized based on N,N-dimethylacrylamide(DMAA),2-acrylamido-2-methylpropane sulfonic acid(AMPS),diallyl dimethyl ammonium chloride(DMDAAC),styrene(ST)and a specialty vinyl monomer(A1).When the concentration of PDA was 3%,the FLAPI of PDA-WBDF was 9.8 mL and the FLHTHP(180℃,3.5 MPa)was 37.8 mL after aging at 240℃for 16 h.In the saturated NaCl environment,the FLAPI of PDA-SWBDF was 4.0 mL and the FLHTHP(180℃,3.5 MPa)was 32.0 mL after aging at 220℃ for 16 h.Under high-temperature and high-salinity conditions,the combined effect of anti-polyelectrolyte and hydrophobic association allowed PDA to adsorb on the bentonite surface tightly.The sulfonic acid groups of PDA increased the negative electronegativity and the hydration film thickness on bentonite surface,which enhanced the colloidal stability,maintained the flattened lamellar structure of bentonite and formed an appropriate particle size distribution,resulting in the formation of dense mud cakes and reducing the filtration loss effectively.展开更多
Zwitterionic polymers are polymers containing a pair of oppositely charged groups in their repeating units,which facilitate the formation of a hydration layer on the surface through ionic solvation.This strong hydrati...Zwitterionic polymers are polymers containing a pair of oppositely charged groups in their repeating units,which facilitate the formation of a hydration layer on the surface through ionic solvation.This strong hydration results in the remarkable properties of zwitterionic polymer hydrogels,including antifouling,lubricating,and anti-freezing capabilities.Owing to these properties,zwitterionic polymer hydrogels have attracted notable attention in biomedical and engineering fields.However,the superhydrophilicity of zwitterionic polymer hydrogels renders them brittle and weak,considerably limiting their use in load-bearing applications.Thus,there is an urgent need to improve the mechanical properties of zwitterionic hydrogels.In this work,we systematically review mechanical enhancement strategies for zwitterionic polymer hydrogels.We cover strate-gies applicable to hybrid and pure high-strength zwitterionic polymer hydrogels.Additionally,we discuss the advantages and limitations of various strength enhancement strategies.展开更多
Optimizing electrolytes is non-trivial and yet promising strategies to simultaneously address dendrite growth and parasitic reactions for aqueous zinc-ion batteries.Herein,we present a low-cost zwitterionic additive,1...Optimizing electrolytes is non-trivial and yet promising strategies to simultaneously address dendrite growth and parasitic reactions for aqueous zinc-ion batteries.Herein,we present a low-cost zwitterionic additive,1-butylsulfonic-3-methylimidazolium(BSM),to enhance conventional ZnSO_(4)electrolytes.Combining experimental characterization and theoretical calculations,the results reveal that the zincophilic sulfonate groups in BSM partially substitute coordinated H_(2)O molecules in the Zn^(2+)hydration shell,thereby optimizing solvation dynamics.Meanwhile,the imidazole groups are preferentially adsorbed onto the zinc anode surface,forming an adaptive layer that guides uniform Zn^(2+)deposition along the(002)crystal orientation,suppresses parasitic reaction,and mitigates dendrite growth.Consequently,the Zn||Zn symmetric cells with BSM electrolyte achieve an exceptional plating/stripping lifespan of 4000 h at 1 mA cm^(-2)(1 mA h cm^(-2))and over 1600 h under elevated current density(5 mA cm^(-2),5 mA h cm^(-2)).Moreover,the Zn||Cu asymmetric cell demonstrates a long cycle life exceeding 1100 cycles while it maintains an average Coulombic efficiency(CE)of above 99.5%.Impressively,the assembled Zn||NH_(4)V_(4)O_(10)(NVO)full cell with BSM modified ZnSO_(4)electrolyte retains 77.6%capacity retention after 1000 cycles at 5 A g^(-1).Thus,this work establishes a dual-regulatory mechanism through zwitterionic additives to enable dendrite-free anodes and ultra-stable aqueous metal batteries.展开更多
In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-ba...In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.展开更多
Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surf...Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surface.Oxygen release has been widely accepted as the ringleader of surficial structure instability.However,the role of TM in surface stability has been much overlooked,not to mention its interplay with oxygen release.Herein,TM dissolution and oxygen release are comparatively investigated in Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2).Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn,facilitating subsequent oxygen release of the ARR process.Intriguingly,surface reorganization occurs following regulated Ni dissolution,enabling the stabilization of the surface and elimination of oxygen release in turn.Accordingly,a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure.Battery performance can be effectively improved,with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle,and cycle stability improved from 66.77%to 90.01%after 100 cycles.This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.展开更多
The rapidly growing electric cars and energy storage systems have extremely promoted the development of advanced lithium and sodium ion batteries and stimulated evolution of high-capacity cathodes.Li/Na-rich layered c...The rapidly growing electric cars and energy storage systems have extremely promoted the development of advanced lithium and sodium ion batteries and stimulated evolution of high-capacity cathodes.Li/Na-rich layered cathodes consisting cationic and anionic reactions as the most typical representative of high-capacity cathodes have shown its tremendous potential.However,there is a long way to go before commercialization because of unsatisfactory performances including large voltage hysteresis,voltage fade and poor cycle performance.Numerous investigations on redox mechanisms and engineering strategies have been performed from the point view of structure and made significant progress,which has been well reviewed.Meanwhile,the unacceptable issues are essentially correlated to the electronic configuration of anionic redox and its interaction with adjacent transition metal cations,which can be well depicted from electronic structure.However,the investigations on anionic reaction process in the viewpoint of electronic structure have been much less summarized.This review aims to compile the current knowledge of anionic redox from the point view of electronic structure,including configuration,origination,evolution,detection and coupling relationship with cationic redox.This work is attempted to inspire new perspectives and design approaches for the development of high-capacity cathodes.展开更多
P3-type manganese-iron-based cathodes with high specific capacity and abundant resource have attracted considerable attention for sodium-ion batteries.However,the long-term cycle stability of P3-type cathodes is still...P3-type manganese-iron-based cathodes with high specific capacity and abundant resource have attracted considerable attention for sodium-ion batteries.However,the long-term cycle stability of P3-type cathodes is still not satisfactory.In this work,we design a new quaternary manganese-iron-based cathode material(P3-Na_(0.54)Mn_(0.64)Fe_(_(0.1)6)Mg_(0.1)Cu_(0.1)O_(2))by Cu substitution.The strong covalent Cu-O bonds improve the structural stability and the reversibility of O redox during charge and discharge processes.Cu substitution also mitigates the structure change with less unit cell volume variation,and improves the Na-ion transport kinetics effectively.As a result,NMFMC delivers much improved cycling stability and rate capability compared with NMFM.It reveals that the charge compensation of NMFMC is mainly contributed by Mn^(3+/4+),Fe^(3+/3.5+)and O_(2-/-)during the charge and discharge processes,and Cu substitution can also enhance the activity and reversibility of Fe redox.This strategy provides a new pathway toward improving the stability and O redox reversibility of P3-type cathode materials for sodium-ion batteries.展开更多
Na_(3)V_(2)(PO_(4))_(2)O_(2)F (VP) is recognized as a promising cathode material for sodium-ion batteries due to its stable structural framework and high specific capacity.Density functional theory (DFT) and finite el...Na_(3)V_(2)(PO_(4))_(2)O_(2)F (VP) is recognized as a promising cathode material for sodium-ion batteries due to its stable structural framework and high specific capacity.Density functional theory (DFT) and finite element simulations show that incorporating SO_(4)^(2-)into VP decreases its band gap,lowers the migration energy barrier,and ensures a uniform Na+concentration gradient and stress distribution during charge and discharge cycles.Consequently,the average Na+diffusion coefficient of Na_(3)V_(2)(PO_(4))_(1.95)(SO_(4))_(0.05)O_(2)F(VPS-1) is roughly double that of VP,leading to enhanced rate capability (80 C,75.5 mAh g^(-1)) and cycling stability (111.0 mAh g^(-1)capacity after 1000 cycles at 10 C current density) for VPS-1.VPS-1 exhibits outstanding fast-charging capabilities,achieving an 80%state of charge in just 8.1 min.The assembled VPS-1//SbSn/NPC full cell demonstrated stable cycling over 200 cycles at a high 5 C current,maintaining an average coulombic efficiency of 95.35%.展开更多
Zwitterions(ZIs)are considered as an ideal,novel ionic conductive medium due to their high dipole moment and good solubility of lithium salts.However,the strong interactions between ZIs and Li^(+)severely hinder Li^(+...Zwitterions(ZIs)are considered as an ideal,novel ionic conductive medium due to their high dipole moment and good solubility of lithium salts.However,the strong interactions between ZIs and Li^(+)severely hinder Li^(+)migration.Herein,a quasi-solid electrolyte(MSQSE-2Na)was fabricated by adding sodium bis(fluorosulfonyl)imide(NaFSI)to sulfobetaine methacrylate(SBMA,a ZI)based polymerization system.Na^(+)occupies the–SO_(3)^(-)site in SBMA prior to Li^(+),which weakens the self-crosslinking of SBMA and frees the Li^(+)bound to the polymer segments.Thus,the polymer conformation of MSQSE-2Na changes to a relaxed,homogeneous"sea-island"type.Meanwhile,Na^(+),due to its electron-withdrawing effect,decreases the electron cloud density of the polymer segments,building a weakly coordinated environment in MSQSE-2Na.Consequently,MSQSE-2Na exhibits excellent ionic conductivity of 7.38×10^(-4)S cm^(-1)and a high Li^(+)transference number of 0.632 at 25℃.The(-)Li|MSQSE-2Na|Li(+)cells exhibit super stability,sustaining operation for over 6182h.The(-)Li|MSQSE-2Na|LiFePO_(4)(+)cells demonstrate outstanding charge/discharge reversibility with a Coulombic efficiency exceeding 99.9%over 270 cycles(≈4500 h),with a capacity retention of 70.0%.This work proposes a new design concept for regulating the polymer conformation and charge characteristics through competitive coordination,thereby advancing the application of ZI-based polymer electrolytes in lithium metal batteries.展开更多
NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe f...NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe framework distortion from interconnected double-octahedral to isolated local octahedral units,as well as a degeneracy of t_(2g) electronic configuration of vanadium(V)3d orbit.In this work,it is clarified that such a degenerate state undergoes spontaneous lattice evolution to reduce the system energy,which causes a low crystalline symmetry and a parasitic V^(4+)/V^(3+)redox reaction in the low-voltage region.Herein,an anion-coordination regulation strategy is developed to suppress this degeneration by anchoring fluorine anions in the double-octahedral[V_(2)O_(8)F_(3)]framework.Density functional theory calculations and in-situ techniques track the F-anion-driven structural evolution and charge compensation mechanisms,revealing that this strategy mitigates detrimental phase segregation during the initial desodiation stage and enhances the Na^(+)diffusion kinetic rate over a factor of 100.Concurrently,this strategy releases the V^(4+)/V^(3+)redox kinetics by eliminating the parasitic low-voltage plateau.The full-cell assembled with the optimized fluorophosphate cathode delivers an increase of 50%in discharge capacity and stable two-voltage-plateau behavior,enabled by its double-octahedral[V_(2)O_(8)F_(3)]polyanionic structure that facilitates unimpeded three-dimensional(3D)Na^(+)transport.By correlating anion-coordination stability with orbital-level charge compensation,this work establishes a universal paradigm for highperformance polyanionic cathodes,positioning it as a competitive candidate for battery applications.展开更多
Aqueous zinc ion batteries(AZIBs)have excellent development prospects due to their high theoretical capacity and low cost.Nevertheless,the commercial separator represented by glass fiber(GF)in AZIBs usually exhibits u...Aqueous zinc ion batteries(AZIBs)have excellent development prospects due to their high theoretical capacity and low cost.Nevertheless,the commercial separator represented by glass fiber(GF)in AZIBs usually exhibits uneven porosity,poor zincophilicity,and insufficient functional groups,resulting in the emergence of the zinc anode dendrites and side reactions.Designing a separator with specific interfacial ion transport behavior is essential to achieve a highly stable reversible zinc anode.Herein,an anionic metal-organic framework(MOF)functionalized separator(GF-Bio-MOF-100)was presented to accelerate the desolvation process and modulate Zn^(2+)flux,thereby delivering the decreased nucleation overpotential and uniform Zn^(2+)deposition.The in-depth kinetics investigations combined with the in-situ Raman spectroscopy demonstrate that the carbonyl group within the Bio-MOF-100 is capable of capturing the H_(2)O molecules of[Zn(H_(2)O)_(6)]^(2+)via the H-bond interaction,which further accelerates the desolvation process and transport kinetics of Zn^(2+).Meanwhile,the anionic framework of the GFBio-MOF-100 separator acts as an interfacial ion channel to regulate the Zn^(2+)flux and enables dendrite-free Zn^(2+)deposition and growth.Consequently,the Zn|GF-Bio-MOF-100|Zn symmetric cell exhibited a stable Zn^(2+)plating/stripping behavior and it could cycle for 2000 h at 0.3 mA cm^(-2).Additionally,the assembled Zn|GF-Bio-MOF-100|MnO_(2)full cell delivers a capacity retention of 83.9% after 1000 cycles at 0.5 A g^(-1).This work provides new insights into the design of functionalized separators for long-life AZIBs.展开更多
Dimethyl carbonate(DMC)is an important chemical raw material extensively used in organic synthesis,lithium-ion battery electrolytes,etc.The primary method for industrial synthesis of DMC involves transesterification b...Dimethyl carbonate(DMC)is an important chemical raw material extensively used in organic synthesis,lithium-ion battery electrolytes,etc.The primary method for industrial synthesis of DMC involves transesterification between ethylene carbonate and MeOH but faces issues with difficult catalyst separation and low catalytic activity.Based on the synergistic catalytic activity of cation and anion,this study develops poly(ionic liquid)s of[N_(X)PIL][PHO]and[N_(3)PIL][Y]with varying alkaline sites and alkalinity levels.This is accomplished by constructing functional polymer monomers containing free radical polymerization sites and nitrogencontaining alkaline groups,and by polymerizing them with suitable crosslinking monomers in a specific ratio before exchanging the resulting polymers with different anions.Results show that doping with nitrogen-containing alkaline groups leads to enhanced basic functional sites while appropriate anions provide intensified alkalinity levels.The[N_(3)PIL][PHO]obtained exhibits superior catalytic activity in transesterification synthesis of DMC,with a yield of 91.43%and selectivity of 99.96%at a reaction time of 2 h.The study also investigates the impact of poly(ionic liquid)cationic structure and anion types,as well as their interactions,on catalytic performance.The findings reveal that the catalytic activity of poly(ionic liquid)is restricted by the interactions between cation and anion.Based on these findings,a possible reaction mechanism was proposed,providing theoretical support for the high-efficiency production of DMC.展开更多
基金financially supported by National Natural Science Foundation of China(No.22302229)Beijing Municipal Excellent Talent Training Funds Youth Advanced Individual Project(No.2018000020124G163)。
文摘Emulsification is one of the important mechanisms of surfactant flooding. To improve oil recovery for low permeability reservoirs, a highly efficient emulsification oil flooding system consisting of anionic surfactant sodium alkyl glucosyl hydroxypropyl sulfonate(APGSHS) and zwitterionic surfactant octadecyl betaine(BS-18) is proposed. The performance of APGSHS/BS-18 mixed surfactant system was evaluated in terms of interfacial tension, emulsification capability, emulsion size and distribution, wettability alteration, temperature-resistance and salt-resistance. The emulsification speed was used to evaluate the emulsification ability of surfactant systems, and the results show that mixed surfactant systems can completely emulsify the crude oil into emulsions droplets even under low energy conditions. Meanwhile,the system exhibits good temperature and salt resistance. Finally, the best oil recovery of 25.45% is achieved for low permeability core by the mixed surfactant system with a total concentration of 0.3 wt%while the molar ratio of APGSHS:BS-18 is 4:6. The current study indicates that the anionic/zwitterionic mixed surfactant system can improve the oil flooding efficiency and is potential candidate for application in low permeability reservoirs.
基金supported by the Australian Research Council(LP220100036)the National Key Research and Development Program(2022YFB2502104 and 2022YFA1602700)+3 种基金the Key Research and Development Program of Jiangsu Provincial Department of Science and Technology of China(BE2022332)the Jiangsu Carbon Peak Carbon Neutralization Science and Technology Innovation Special Fund(BE2022605)the Australian Research Council for his Discovery Early Career Researcher Award fellowship(DE230101105)the China Scholarship Council(CSC,grant no.202306190185)for funding a scholarship。
文摘Zwitterionic materials with covalently tethered cations and anions have great potential as electrolyte additives for aqueous Znion batteries(AZIBs)owing to their appealing intrinsic characteristics and merits.However,the impact of cationic and anionic moieties within zwitterions on enhancing the performance of AZIBs remains poorly understood.Herein,three zwitterions,namely carboxybetaine methacrylate(CBMA),sulfobetaine methacrylate(SBMA),and 2-methacryloyloxyethyl phosphorylcholine(MPC),were selected as additives to investigate their different action mechanisms in AZIBs.All three zwitterions have the same quaternary ammonium as the positively charged group,but having different negatively charged segments,i.e.,carboxylate,sulfonate,and phosphate for CBMA,SBMA,and MPC,respectively.By systematical electrochemical analysis,these zwitterions all contribute to enhanced cycling life of Zn anode,with MPC having the most pronounced effect,which can be attributed to the synergistic effect of positively quaternary ammonium group and unique negatively phosphate groups.As a result,the Zn//Zn cell with MPC as additive in ZnSO_(4)electrolyte exhibits an ultralong lifespan over 5000 h.This work proposes new insights to the future development of multifunctional zwitterionic additives for remarkably stable AZIBs.
文摘Lysozyme,myoglobin and BSA were used as models of globular proteins covering a wide range of pl.The purpose is to extend the studies to anionic lipid bilayers.Electrostatics is studied in cationic protein adsorption to zwitterionic PC and anionic mixed PC/PG SUVs.Protein adsorption is investigated in SUVs along with changes of fluorescence emission spectra.Partition coefficients and cooperativity parameters are calculated.At pl binding obtains maximum while at lower or higher pHs binding decreases.In Gouy-Chapman formalism activity coefficient goes with square charge,which deviations indicate asymmetric location of anionic phospholipid in the inner leaflet,in mixed SUVs for lysozyme-and myoglobin-PC/PG systems,in agreement with experiments and molecular dynamics simulations.Vesicles bind myoglobin anti-cooperatively while lysozyme-BSA cooperativitivey.A model is proposed for both,which composes two protein sub-layers with different structures and properties.Hill coefficient reflects subunit cooperativity of bi and tridomain proteins.
基金supported by the National Natural Science Foundation of China(Nos.T2222013 and 52073203)Tianjin Natural Science Foundation(No.22JCQNJC01040)the State Key Laboratory of Molecular Engineering of Polymers(Fudan University)(No.K2024-19).
文摘Flexible strain sensors have received tremendous attention because of their potential applications as wearable sensing devices.However, the integration of key functions into a single sensor, such as high stretchability, low hysteresis, self-adhesion, andexcellent antifreezing performance, remains an unmet challenge. In this respect, zwitterionic hydrogels have emerged asideal material candidates for breaking through the above dilemma. The mechanical properties of most reported zwitterionichydrogels, however, are relatively poor, significantly restricting their use under load-bearing conditions. Traditional improve-ment approaches often involve complex preparation processes, making large-scale production challenging. Additionally,zwitterionic hydrogels prepared with chemical crosslinkers are typically fragile and prone to irreversible deformation underlarge strains, resulting in the slow recovery of structure and function. To fundamentally enhance the mechanical properties ofpure zwitterionic hydrogels, the most effective approach is the regulation of the chemical structure of zwitterionic monomersthrough a targeted design strategy. This study employed a novel zwitterionic monomer carboxybetaine urethane acrylate(CBUTA), which contained one urethane group and one carboxybetaine group on its side chain. Through the direct polym-erization of ultrahigh concentration monomer solutions without adding any chemical crosslinker, we successfully developedpure zwitterionic supramolecular hydrogels with significantly enhanced mechanical properties, self-adhesive behavior, andantifreezing performance. Most importantly, the resultant zwitterionic hydrogels exhibited high tensile strength and tough-ness and displayed ultralow hysteresis under strain conditions up to 1100%. This outstanding performance was attributedto the unique liquid–liquid phase separation phenomenon induced by the ultrahigh concentration of CBUTA monomers inan aqueous solution, as well as the enhanced polymer chain entanglement and the strong hydrogen bonds between urethanegroups on the side chains. The potential application of hydrogels in strain sensors and high-performance triboelectric nano-generators was further explored. Overall, this work provides a promising strategy for developing pure zwitterionic hydrogelsfor flexible strain sensors and self-powered electronic devices.
基金financially supported by the National Key Research and Development Program of China(2022YFE0138900)the National Natural Science Foundation of China(21972017)+1 种基金the Fundamental Research Funds for the Central Universities of Ministry of Education of China(D5000240188)the"Scientific and Technical Innovation Action Plan"Basic Research Field of Shanghai Science and Technology Committee(19JC1410500)。
文摘Traditional hydrogels are inevitably damaged during practical applications,resulting in a gradual deterioration of their functional efficacy.A primary strategy to address this issue involves developing hydrogels with inherent self-healing properties.In this study,we report the synthesis of self-healing polyacrylate hydrogels that integrate zwitterions,hydrophilic nano-silica and aluminum ions.Due to the synergistic effect of multiple hydrogen bonds,coordination bonds and electrostatic interactions,the tensile strength of the hydrogel is enhanced from 15.1 to 162.6 kPa.Moreover,the electrical resistance and tensile strength of the hydrogel can almost recover to its initial values after 20 min of healing at room temperature,exhibiting remarkable self-healing performance.Furthermore,the zwitterionic polyacrylate hydrogel serves as a wearable sensor with the capability of accurately response to the bending and stretching of human joints,exhibting a gauge factor of 1.87 under tensile strain ranging from 80% to 100%.Even after being freezed at-20℃ for 3 h,the zwitterionic polyacrylate hydrogel retains its exceptional writing performance.In conclusion,the hydrogels developed in this study demonstrate significant potential for wearable electronics applications.
基金supported by the Beijing Natural Science Foundation(No.7222261)CAMS Innovation Fund for Medical Sciences(No.2022-I2M-1-015)。
文摘The objective of this study was to predict,screen,synthesize,and investigate cocrystals of poorly soluble flavonoids that are commonly found in dietary supplements with bipolar compound picolinic acid(PA).To improve the efficiency and success rate of experimental screening,two virtual tools based on hydrogen bond propensity(HBP)and modified molecular electrostatic potential(MEP)maps were used.The prediction accuracy of HBP and MEP is 58.82%and 94.11%,respectively,presenting that the MEP model is very powerful in the discovery of pharmaceutical cocrystals.Among the 12 successfully obtained cocrystals,4 single crystals of PA with luteolin(LUT),genistein(GEN),taxifolin(TAX),dihydromyricetin(DHM)were obtained for the first time.Charged-assisted O-H…O and N-H…O hydrogen bonds appear as main hydrogen bonding synthons,and PA adopts a zwitterionic form after cocrystallization.GEN-PA,TAX-PA,and DHM-PA showed higher DPPH'radical-scavenging capacities;LUT-PA and DHM-PA showed higher ABTS^(+)radical-scavenging capacities;GEN-PA and DHM-PA possessed better protective effects on H9c2 cells from hypoxic injury caused by CoCl_(2)than corresponding pure flavonoids.
基金supported by the National Natural Science Foundation of China(Grant No.52403305)the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB0880000)+1 种基金Tianchi Talent Program of Xinjiang Uygur Autonomous Region(Grant No.2024000068)Postdoctoral Fellow-ship Program(Grade C)(Grant No.GZC20232959)。
文摘The prediction of new fluorooxoborates as ultraviolet(UV)/deep ultraviolet(DUV)opto-electronic functional materials from a largely unexplored chemical space is a challenging task.It has been suggested that the anionic frameworks formed by B–O and B–O–F units significantly determine the physical properties of fluorooxoborates.Therefore,the rational design of anionic frameworks could facilitate the materials discovery process.Herein,we propose that a candidate anionic framework can be efficiently derived from an existing one by slightly altering its oxygen content.Following this idea,we hypothesized the existence of a 1D[B_(3)O_(5)F]_(∞)chain from the wellknown 2D[B_(6)O_(9)F_(2_)]_(∞)layer.Accordingly,seven CaB_(3)O_(5)F structures with the expected anionic framework were successfully predicted.First-principles calculations show that all these structures have potential in the UV/DUV birefringent or nonlinear optical(NLO)material field,indicating that the 1D[B_(3)O_(5)F]_(∞)chain is indeed a promising anionic framework for achieving UV/DUV birefringent and NLO performance.
基金funding support from the National Science Fund for Distinguished Young Scholars(Grant No.T2225027)the National Natural Science Foundation of China(Grant Nos.12074013 and 12204419)the China Postdoctoral Science Foundation(Grant No.2021M702956)。
文摘Electrides,characterized by spatially confined anionic electrons,have emerged as a promising class of materials for catalysis,magnetism,and superconductivity.However,transition-metal-based electrides with diverse electron dimensionalities remain largely unexplored.Here,we perform a comprehensive first-principles investigation of Y-Co electrides,focusing on Y_(3)Co,Y_(3)Co_(2),and YCo.Our calculations reveal a striking dimensional evolution of anionic electrons:from two-dimensional(2D)confinement in YCo to one-dimensional(1D)in Y_(3)Co_(2)and zero-dimensional(0D)in Y_(3)Co.Remarkably,the YCo monolayer exhibits intrinsic ferromagnetism,with a magnetic moment of 0.65μB per formula unit arising from spin-polarized anionic electrons mediating long-range coupling between Y and Co ions.The monolayer also shows a low exfoliation energy(1.66 J/m^(2)),indicating experimental feasibility.All three electrides exhibit low work functions(2.76 eV-3.11 eV)along with Co-centered anionic states.This work expands the family of transition-metal-based electrides and highlights dimensionality engineering as a powerful strategy for tuning electronic and magnetic properties.
基金supported by State Key Laboratory of Deep Oil and Gas(No.SKLDOG2024-ZYRC-03)supported by the Excellent Young Scientists Fund of the National Natural Science Foundation of China(No.52322401)the National Natural Science Foundation of China(52288101).
文摘As the global exploration and development of oil and gas resources advances into deep formations,the harsh conditions of high temperature and high salinity present significant challenges for drilling fluids.In order to address the technical difficulties associated with the failure of filtrate loss reducers under high-temperature and high-salinity conditions.In this study,a hydrophobic zwitterionic filtrate loss reducer(PDA)was synthesized based on N,N-dimethylacrylamide(DMAA),2-acrylamido-2-methylpropane sulfonic acid(AMPS),diallyl dimethyl ammonium chloride(DMDAAC),styrene(ST)and a specialty vinyl monomer(A1).When the concentration of PDA was 3%,the FLAPI of PDA-WBDF was 9.8 mL and the FLHTHP(180℃,3.5 MPa)was 37.8 mL after aging at 240℃for 16 h.In the saturated NaCl environment,the FLAPI of PDA-SWBDF was 4.0 mL and the FLHTHP(180℃,3.5 MPa)was 32.0 mL after aging at 220℃ for 16 h.Under high-temperature and high-salinity conditions,the combined effect of anti-polyelectrolyte and hydrophobic association allowed PDA to adsorb on the bentonite surface tightly.The sulfonic acid groups of PDA increased the negative electronegativity and the hydration film thickness on bentonite surface,which enhanced the colloidal stability,maintained the flattened lamellar structure of bentonite and formed an appropriate particle size distribution,resulting in the formation of dense mud cakes and reducing the filtration loss effectively.
基金supported by the National Natural Science Foundation of China(Nos.T2222013,52233008 and 52073203).
文摘Zwitterionic polymers are polymers containing a pair of oppositely charged groups in their repeating units,which facilitate the formation of a hydration layer on the surface through ionic solvation.This strong hydration results in the remarkable properties of zwitterionic polymer hydrogels,including antifouling,lubricating,and anti-freezing capabilities.Owing to these properties,zwitterionic polymer hydrogels have attracted notable attention in biomedical and engineering fields.However,the superhydrophilicity of zwitterionic polymer hydrogels renders them brittle and weak,considerably limiting their use in load-bearing applications.Thus,there is an urgent need to improve the mechanical properties of zwitterionic hydrogels.In this work,we systematically review mechanical enhancement strategies for zwitterionic polymer hydrogels.We cover strate-gies applicable to hybrid and pure high-strength zwitterionic polymer hydrogels.Additionally,we discuss the advantages and limitations of various strength enhancement strategies.
基金financially supported by the National Natural Science Foundation of China(No.21703152,21801136,52025013,and 22121005)the National Key R&D Program of China(2021YFB4000200)the Natural Science Foundation of Tianjin(No.19JCQNJC02000)。
文摘Optimizing electrolytes is non-trivial and yet promising strategies to simultaneously address dendrite growth and parasitic reactions for aqueous zinc-ion batteries.Herein,we present a low-cost zwitterionic additive,1-butylsulfonic-3-methylimidazolium(BSM),to enhance conventional ZnSO_(4)electrolytes.Combining experimental characterization and theoretical calculations,the results reveal that the zincophilic sulfonate groups in BSM partially substitute coordinated H_(2)O molecules in the Zn^(2+)hydration shell,thereby optimizing solvation dynamics.Meanwhile,the imidazole groups are preferentially adsorbed onto the zinc anode surface,forming an adaptive layer that guides uniform Zn^(2+)deposition along the(002)crystal orientation,suppresses parasitic reaction,and mitigates dendrite growth.Consequently,the Zn||Zn symmetric cells with BSM electrolyte achieve an exceptional plating/stripping lifespan of 4000 h at 1 mA cm^(-2)(1 mA h cm^(-2))and over 1600 h under elevated current density(5 mA cm^(-2),5 mA h cm^(-2)).Moreover,the Zn||Cu asymmetric cell demonstrates a long cycle life exceeding 1100 cycles while it maintains an average Coulombic efficiency(CE)of above 99.5%.Impressively,the assembled Zn||NH_(4)V_(4)O_(10)(NVO)full cell with BSM modified ZnSO_(4)electrolyte retains 77.6%capacity retention after 1000 cycles at 5 A g^(-1).Thus,this work establishes a dual-regulatory mechanism through zwitterionic additives to enable dendrite-free anodes and ultra-stable aqueous metal batteries.
基金National Key Research and Development Program of China,Grant/Award Number:2022YFB2502000National Natural Science Foundation of China,Grant/Award Number:52207244。
文摘In the realm of sodium-ion batteries(SIBs),Mn-based layered oxide cathodes have garnered considerable attention owing to their anionic redox reactions(ARRs).Compared to other types of popular sodium-ion cathodes,Mn-based layered oxide cathodes with ARRs exhibit outstanding specific capacity and energy density,making them promising for SIB applications.However,these cathodes still face some scientific challenges that need to be addressed.This review systematically summarizes the composition,structure,oxygen-redox mechanism,and performance of various types of Mn-based cathodes with ARRs,as well as the main scientific challenges they face,including sluggish ion diffusion,cationic migration,O_(2) release,and element dissolution.Currently,to resolve these challenges,efforts mainly focus on six aspects:synthesis methods,structural design,doped modification,electrolyte design,and surface engineering.Finally,this review provides new insights for future direction,encompassing both fundamental research,such as novel cathode types,interface optimization,and interdisciplinary research,and considerations from an industrialization perspective,including scalability,stability,and safety.
基金supported by the National Key Research and Development Program (2019YFA0405601)National Science Foundation of China(No. 22309097, 22179066, 21902179)+1 种基金Shandong Provincial Natural Science Foundation (2023KJ228, ZR2021QE061, ZR202103010205)the Startup Foundation for Advanced Talents in Qingdao University (DC2000005106)
文摘Anionic redox reaction(ARR)can provide extra capacity beyond transition metal(TM)redox in lithium-rich TM oxide cathodes.Practical ARR application is much hindered by the structure instability,particularly at the surface.Oxygen release has been widely accepted as the ringleader of surficial structure instability.However,the role of TM in surface stability has been much overlooked,not to mention its interplay with oxygen release.Herein,TM dissolution and oxygen release are comparatively investigated in Li_(1.2)Ni_(0.2)Mn_(0.6)O_(2).Ni is verified to detach from the lattice counter-intuitively despite the overwhelming stoichiometry of Mn,facilitating subsequent oxygen release of the ARR process.Intriguingly,surface reorganization occurs following regulated Ni dissolution,enabling the stabilization of the surface and elimination of oxygen release in turn.Accordingly,a novel optimization strategy is proposed by adding a relaxation step at 4.50 V within the first cycle procedure.Battery performance can be effectively improved,with voltage decay suppressed from 3.44 mV/cycle to 1.60 mV/cycle,and cycle stability improved from 66.77%to 90.01%after 100 cycles.This work provides new perspectives for clarifying ARR surface instability and guidance for optimizing ARR performance.
基金financially supported by the National Key Research and Development Program of China(No.2019YFA0405601)the National Natural Science Foundation of China(No.52130202)the Scientific Research Foundation for High-level Talents of Anhui University of Science and Technology(No.2022yjrc105)。
文摘The rapidly growing electric cars and energy storage systems have extremely promoted the development of advanced lithium and sodium ion batteries and stimulated evolution of high-capacity cathodes.Li/Na-rich layered cathodes consisting cationic and anionic reactions as the most typical representative of high-capacity cathodes have shown its tremendous potential.However,there is a long way to go before commercialization because of unsatisfactory performances including large voltage hysteresis,voltage fade and poor cycle performance.Numerous investigations on redox mechanisms and engineering strategies have been performed from the point view of structure and made significant progress,which has been well reviewed.Meanwhile,the unacceptable issues are essentially correlated to the electronic configuration of anionic redox and its interaction with adjacent transition metal cations,which can be well depicted from electronic structure.However,the investigations on anionic reaction process in the viewpoint of electronic structure have been much less summarized.This review aims to compile the current knowledge of anionic redox from the point view of electronic structure,including configuration,origination,evolution,detection and coupling relationship with cationic redox.This work is attempted to inspire new perspectives and design approaches for the development of high-capacity cathodes.
基金supported by the National Key Scientific Research Project(No.2022YFB2502300)the National Natural Science Foundation of China(No.52071085).
文摘P3-type manganese-iron-based cathodes with high specific capacity and abundant resource have attracted considerable attention for sodium-ion batteries.However,the long-term cycle stability of P3-type cathodes is still not satisfactory.In this work,we design a new quaternary manganese-iron-based cathode material(P3-Na_(0.54)Mn_(0.64)Fe_(_(0.1)6)Mg_(0.1)Cu_(0.1)O_(2))by Cu substitution.The strong covalent Cu-O bonds improve the structural stability and the reversibility of O redox during charge and discharge processes.Cu substitution also mitigates the structure change with less unit cell volume variation,and improves the Na-ion transport kinetics effectively.As a result,NMFMC delivers much improved cycling stability and rate capability compared with NMFM.It reveals that the charge compensation of NMFMC is mainly contributed by Mn^(3+/4+),Fe^(3+/3.5+)and O_(2-/-)during the charge and discharge processes,and Cu substitution can also enhance the activity and reversibility of Fe redox.This strategy provides a new pathway toward improving the stability and O redox reversibility of P3-type cathode materials for sodium-ion batteries.
基金National Natural Science Foundation of China (52372224 and 52072299)Major Project of Shaanxi Coal Joint Fund of Shaanxi Provincial Science and Technology Department (2019JLZ-07)。
文摘Na_(3)V_(2)(PO_(4))_(2)O_(2)F (VP) is recognized as a promising cathode material for sodium-ion batteries due to its stable structural framework and high specific capacity.Density functional theory (DFT) and finite element simulations show that incorporating SO_(4)^(2-)into VP decreases its band gap,lowers the migration energy barrier,and ensures a uniform Na+concentration gradient and stress distribution during charge and discharge cycles.Consequently,the average Na+diffusion coefficient of Na_(3)V_(2)(PO_(4))_(1.95)(SO_(4))_(0.05)O_(2)F(VPS-1) is roughly double that of VP,leading to enhanced rate capability (80 C,75.5 mAh g^(-1)) and cycling stability (111.0 mAh g^(-1)capacity after 1000 cycles at 10 C current density) for VPS-1.VPS-1 exhibits outstanding fast-charging capabilities,achieving an 80%state of charge in just 8.1 min.The assembled VPS-1//SbSn/NPC full cell demonstrated stable cycling over 200 cycles at a high 5 C current,maintaining an average coulombic efficiency of 95.35%.
基金supported by the National Natural Science Foundation of China(22078228)。
文摘Zwitterions(ZIs)are considered as an ideal,novel ionic conductive medium due to their high dipole moment and good solubility of lithium salts.However,the strong interactions between ZIs and Li^(+)severely hinder Li^(+)migration.Herein,a quasi-solid electrolyte(MSQSE-2Na)was fabricated by adding sodium bis(fluorosulfonyl)imide(NaFSI)to sulfobetaine methacrylate(SBMA,a ZI)based polymerization system.Na^(+)occupies the–SO_(3)^(-)site in SBMA prior to Li^(+),which weakens the self-crosslinking of SBMA and frees the Li^(+)bound to the polymer segments.Thus,the polymer conformation of MSQSE-2Na changes to a relaxed,homogeneous"sea-island"type.Meanwhile,Na^(+),due to its electron-withdrawing effect,decreases the electron cloud density of the polymer segments,building a weakly coordinated environment in MSQSE-2Na.Consequently,MSQSE-2Na exhibits excellent ionic conductivity of 7.38×10^(-4)S cm^(-1)and a high Li^(+)transference number of 0.632 at 25℃.The(-)Li|MSQSE-2Na|Li(+)cells exhibit super stability,sustaining operation for over 6182h.The(-)Li|MSQSE-2Na|LiFePO_(4)(+)cells demonstrate outstanding charge/discharge reversibility with a Coulombic efficiency exceeding 99.9%over 270 cycles(≈4500 h),with a capacity retention of 70.0%.This work proposes a new design concept for regulating the polymer conformation and charge characteristics through competitive coordination,thereby advancing the application of ZI-based polymer electrolytes in lithium metal batteries.
基金supported by the National Key Research and Development Program of China(2023YFB2406100)the National Natural Science Foundation of China(Grant No.22075062 and U23A20573)+6 种基金the Heilongjiang Touyan Team(Grant No.HITTY20190033)the Heilongjiang Postdoctoral Financial Assistance(Grant No.LBH-Z23137)the Postdoctoral Fellowship Program of CPSF(Grant No.GZC20233448)the China Postdoctoral Science Foundation(Grant No.2024M754198)the Shenzhen Science and Technology Program(KCXST20221021111216037)the Fundamental Research Funds for the Central Universities(Grant No.FRFCU5710051922)the program of “Open bidding for selecting the best candidates”(Grant No.2023JCA06)from Jiangxi Fuzhou Municipal Government。
文摘NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe framework distortion from interconnected double-octahedral to isolated local octahedral units,as well as a degeneracy of t_(2g) electronic configuration of vanadium(V)3d orbit.In this work,it is clarified that such a degenerate state undergoes spontaneous lattice evolution to reduce the system energy,which causes a low crystalline symmetry and a parasitic V^(4+)/V^(3+)redox reaction in the low-voltage region.Herein,an anion-coordination regulation strategy is developed to suppress this degeneration by anchoring fluorine anions in the double-octahedral[V_(2)O_(8)F_(3)]framework.Density functional theory calculations and in-situ techniques track the F-anion-driven structural evolution and charge compensation mechanisms,revealing that this strategy mitigates detrimental phase segregation during the initial desodiation stage and enhances the Na^(+)diffusion kinetic rate over a factor of 100.Concurrently,this strategy releases the V^(4+)/V^(3+)redox kinetics by eliminating the parasitic low-voltage plateau.The full-cell assembled with the optimized fluorophosphate cathode delivers an increase of 50%in discharge capacity and stable two-voltage-plateau behavior,enabled by its double-octahedral[V_(2)O_(8)F_(3)]polyanionic structure that facilitates unimpeded three-dimensional(3D)Na^(+)transport.By correlating anion-coordination stability with orbital-level charge compensation,this work establishes a universal paradigm for highperformance polyanionic cathodes,positioning it as a competitive candidate for battery applications.
基金supported by the National Natural Science Foundation of China(No.22278328)the Key Research and Development Program of Shaanxi Province(No.2023-YBGY-292)。
文摘Aqueous zinc ion batteries(AZIBs)have excellent development prospects due to their high theoretical capacity and low cost.Nevertheless,the commercial separator represented by glass fiber(GF)in AZIBs usually exhibits uneven porosity,poor zincophilicity,and insufficient functional groups,resulting in the emergence of the zinc anode dendrites and side reactions.Designing a separator with specific interfacial ion transport behavior is essential to achieve a highly stable reversible zinc anode.Herein,an anionic metal-organic framework(MOF)functionalized separator(GF-Bio-MOF-100)was presented to accelerate the desolvation process and modulate Zn^(2+)flux,thereby delivering the decreased nucleation overpotential and uniform Zn^(2+)deposition.The in-depth kinetics investigations combined with the in-situ Raman spectroscopy demonstrate that the carbonyl group within the Bio-MOF-100 is capable of capturing the H_(2)O molecules of[Zn(H_(2)O)_(6)]^(2+)via the H-bond interaction,which further accelerates the desolvation process and transport kinetics of Zn^(2+).Meanwhile,the anionic framework of the GFBio-MOF-100 separator acts as an interfacial ion channel to regulate the Zn^(2+)flux and enables dendrite-free Zn^(2+)deposition and growth.Consequently,the Zn|GF-Bio-MOF-100|Zn symmetric cell exhibited a stable Zn^(2+)plating/stripping behavior and it could cycle for 2000 h at 0.3 mA cm^(-2).Additionally,the assembled Zn|GF-Bio-MOF-100|MnO_(2)full cell delivers a capacity retention of 83.9% after 1000 cycles at 0.5 A g^(-1).This work provides new insights into the design of functionalized separators for long-life AZIBs.
基金supported by the National Natural Science Foundation of China(Grant No.22278077,22408209 and 22108040)National Key Research and Development Program of China(Grant No.2022YFB4101800)+2 种基金Key Program of Qingyuan Innovation Laboratory(Grant No.00221004)Research Program of Qingyuan Innovation Laboratory(Grant No.00523006)Natural Science Foundation of Fujian Province(Grant No.2022J02019,2024J011550).
文摘Dimethyl carbonate(DMC)is an important chemical raw material extensively used in organic synthesis,lithium-ion battery electrolytes,etc.The primary method for industrial synthesis of DMC involves transesterification between ethylene carbonate and MeOH but faces issues with difficult catalyst separation and low catalytic activity.Based on the synergistic catalytic activity of cation and anion,this study develops poly(ionic liquid)s of[N_(X)PIL][PHO]and[N_(3)PIL][Y]with varying alkaline sites and alkalinity levels.This is accomplished by constructing functional polymer monomers containing free radical polymerization sites and nitrogencontaining alkaline groups,and by polymerizing them with suitable crosslinking monomers in a specific ratio before exchanging the resulting polymers with different anions.Results show that doping with nitrogen-containing alkaline groups leads to enhanced basic functional sites while appropriate anions provide intensified alkalinity levels.The[N_(3)PIL][PHO]obtained exhibits superior catalytic activity in transesterification synthesis of DMC,with a yield of 91.43%and selectivity of 99.96%at a reaction time of 2 h.The study also investigates the impact of poly(ionic liquid)cationic structure and anion types,as well as their interactions,on catalytic performance.The findings reveal that the catalytic activity of poly(ionic liquid)is restricted by the interactions between cation and anion.Based on these findings,a possible reaction mechanism was proposed,providing theoretical support for the high-efficiency production of DMC.
