Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries(SSBs),due to their high safety and long operation life span.However,the two major factors that impede the expec...Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries(SSBs),due to their high safety and long operation life span.However,the two major factors that impede the expected performance of batteries are:the easy formation of lithium dendrites due to the concentration gradient of anions,and the low ionic conductivity at room temperature,which prevents reaching ideal electrochemical performance.Single-ion quasi-solid-state electrolytes(SIQSSEs)could provide higher safety and energy density,owing to absence of anion concentration gradient and solvent,as well as good lithium-ion transport ability.The porous covalent organic frameworks(COFs)are beneficial for con-structing appropriate lithium-ion transport pathway,due to the ordered 1D channel.In addition,the boroxine COFs(COF-5)offers strong ability of withdrawing anion part of lithium salt.Last but not the least,boron atom could play the role of coordinate site due to its electron deficiency.These advantages afford an opportunity to obtain a SIQSSE with high ionic conductivity and high lithium transference number(LTN)simultaneously.The COF-5 based SIQSSEs delivered a high ionic conductivity of 6.3×10^(-4)S·cm^(-1),with a high LTN of 0.92 and a wide electrochemical stable window(ESW)of 4.7 V at room temperature.The LiFePO4(LFP)/Li cells,which was assembled with COF-5 based SIQSSE,exhibited outstanding long cycle stability,high initial capacity and favorable rate performance.The results indicated COFs could be an ideal material for single-ion solid-state electrolytes in next-generation batteries.展开更多
While single-ion conducting solid polymer electrolytes(SPE)offer inherent safety advantages for lithium metal batteries,their practical implementation is hindered by inadequate ionic transport and unstable electrode i...While single-ion conducting solid polymer electrolytes(SPE)offer inherent safety advantages for lithium metal batteries,their practical implementation is hindered by inadequate ionic transport and unstable electrode interfaces.We presented a breakthrough single-ion SPE system through molecular engineering of lithium-enriched porous aromatic frameworks(PAF-228-Li)integrated with poly(ethylene oxide),achieving exceptional ion conduction and interfacial stability.The precisely designed PAF-228-Li architecture established continuous 3D Li+transport pathways through its intrinsic porous channels and surface conduction sites,synergistically enhanced by PVDF-HFP nanofiber networks.This unique design enabled record-high ionic conductivities of 5.48×10^(-4)S cm^(-1)at 30℃and 3.4×10^(-4)S cm^(-1)at-20℃—among the best reported for PEO-based SPEs.The electrolyte spontaneously formed a selflimiting SEI rich in LiF/Li3N,effectively suppressing dendritic growth while enabling unprecedented cycling stability:Li||LiFePO4cells maintain 83.7%capacity over 700 cycles(30℃)and deliver 104.4 mA h g^(-1)after 1100 cycles at-20℃.Practical viability is further demonstrated in pouch cell configurations with stable operation at 30℃.This work pioneers a materials paradigm combining porous framework engineering with polymer electrolyte design,establishing new researching direction for low-temperature compatible,dendrite-resistant solid-state batteries.展开更多
Single ion gel polymer electrolyte has the advantages of high Li^(+)conductivity and dendrite mitigation.However,the addition of organic solvent makes the electrolyte flammable,posing serious safety hazards.Herein,we ...Single ion gel polymer electrolyte has the advantages of high Li^(+)conductivity and dendrite mitigation.However,the addition of organic solvent makes the electrolyte flammable,posing serious safety hazards.Herein,we report a flame-retard ant cross-linked sp^(3)boron-based single-ion gel polymer electrolyte(BSIPE).BSIPE was prepared by a simple one-step photoinitiated in situ thiol-ene click reaction.Due to the boron-based anions being immobilized in the cross-linking network,the developed BSIPE/PFN exhibits a high t_(Li^(+))(0.87),which can mitigate concentration polarization phenomenon and suppress the growth of lithium dendrites.BSIPE/PFN plasticized with triethyl phosphate(TEP),fluoroethylene carbonate(FEC)and LiNO_(3)exhibits enhanced ionic conductivity of 4.25×10^(-4)S cm^(-1)at 30℃ and flame retardancy.FEC and LiNO_(3) are conducive to form a stable solid electrolyte interphase(SEI)rich in Li_(3)N and LiF to improve interface stability.As expected,the dendrite-free Li‖BSIPE/PFN‖Li symmetric cell exhibits considerable cycling life over 1500 h.BSIPE/PFN significantly boosts the performance of LFP‖Li cell,which displays a capacity retention of 84.6%after 500 cycles.The BSIPE/PFN has promising applications in highsafety and high-performance lithium metal batteries.展开更多
The practical application of rechargeable lithium metal batteries(LMBs) encounters significant challenges due to the notorious dendrite growth triggered by uneven Li deposition behaviors. In this work,a mechanically r...The practical application of rechargeable lithium metal batteries(LMBs) encounters significant challenges due to the notorious dendrite growth triggered by uneven Li deposition behaviors. In this work,a mechanically robust and single-ion-conducting interfacial layer, fulfilled by the strategic integration of flexible cellulose acetate(CA) matrix with rigid graphene oxide(GO) and Li F fillers(termed the CGL layer), is rationally devised to serve as a stabilizer for dendrite-free lithium(Li) metal batteries. The GCL film exhibits favorable mechanical properties with high modulus and flexibility that help to relieve interface fluctuations. More crucially, the electron-donating carbonyl groups(C=O) enriched in GCL foster a strengthened correlation with Li^(+), which availably aids the Li^(+)desolvation process and expedites facile Li^(+)mobility, yielding exceptional Li^(+) transference number of 0.87. Such single-ion conductive properties regulate rapid and uniform interfacial transport kinetics, mitigating the growth of Li dendrites and the decomposition of electrolytes. Consequently, stable Li anode with prolonged cycle stabilities and flat deposition morphologies are realized. The Li||LiFePO_(4) full cells with CGL protective layer render an outstanding cycling capability of 500 cycles at 3 C, and an ultrahigh capacity retention of 99.99% for over 220 cycles even under harsh conditions. This work affords valuable insights into the interfacial regulation for achieving high-performance LMBs.展开更多
With the depletion of fossil fuels and the demand for high-performance energy storage devices,solidstate lithium metal batteries have received widespread attention due to their high energy density and safety advantage...With the depletion of fossil fuels and the demand for high-performance energy storage devices,solidstate lithium metal batteries have received widespread attention due to their high energy density and safety advantages.Among them,the earliest developed organic solid-state polymer electrolyte has a promising future due to its advantages such as good mechanical flexibility,but its poor ion transport performance dramatically limits its performance improvement.Therefore,single-ion conducting polymer electrolytes(SICPEs)with high lithium-ion transport number,capable of improving the concentration polarization and inhibiting the growth of lithium dendrites,have been proposed,which provide a new direction for the further development of high-performance organic polymer electrolytes.In view of this,lithium ions transport mechanisms and design principles in SICPEs are summarized and discussed in this paper.The modification principles currently used can be categorized into the following three types:enhancement of lithium salt anion-polymer interactions,weakening of lithium salt anion-cation interactions,and modulation of lithium ion-polymer interactions.In addition,the advances in single-ion conductors of conventional and novel polymer electrolytes are summarized,and several typical highperformance single-ion conductors are enumerated and analyzed in what way they improve ionic conductivity,lithium ions mobility,and the ability to inhibit lithium dendrites.Finally,the advantages and design methodology of SICPEs are summarized again and the future directions are outlined.展开更多
Lithium metal is deemed as an ideal anode material in lithium-ion batteries because of its ultrahigh theoretical specific capacity and the lowest redox potential.However,the rapid capacity attenuation and inferior sec...Lithium metal is deemed as an ideal anode material in lithium-ion batteries because of its ultrahigh theoretical specific capacity and the lowest redox potential.However,the rapid capacity attenuation and inferior security resulting from the dendritic lithium growth severely limit its commercialization.Herein a novel hybrid gel polymer electrolyte (GPE) based on electrospun lithium sulfonated polyoxadiazole (LiSPOD) nanofibrous membrane swelled by lithium bis(trifluoromethanesulfonyl)imide (Li TFSI) ether liquid electrolyte is proposed to address the issue of lithium dendrites.The Li-SPOD membrane synthesized by a simple one-pot method exhibits excellent mechanical strength and thermal resistance due to its high molecular weight and rigid backbone.The electron-withdrawing oxadiazole ring and oxadiazole ring-Li;complex,and N,O heteroatoms with lone pairs of electrons in Li-SPOD macromolecular chains facilitate the dissociation of-SO_(3)Li group and Li^(+)transference.The hybrid Li-SPOD GPE exhibits both a high lithium-ion transference number (0.64) and high ionic conductivity (2.03 m S/cm) as well as superior interfacial compacity with lithium anodes.The Li Fe PO_(4)-Li cell using this novel GPE can operate steadily at 2C for 300 cycles,remaining a high discharge capacity of 125 m Ah/g and dendrite-free anode.Remarkable performance improvements for the Li-Li and Cu-Li cells are also presented.展开更多
We use the mean-field approximation of Dyson–Maleev representation to study an XXZ Heisenberg ferrimagnetic spin chain with single-ion anisotropy. By solving the self-consistent equations with different anisotropies,...We use the mean-field approximation of Dyson–Maleev representation to study an XXZ Heisenberg ferrimagnetic spin chain with single-ion anisotropy. By solving the self-consistent equations with different anisotropies, λ and D respectively,the energy spectrums, internal energy, static susceptibility and specific heat are calculated. Especially, the quantum phase transition of the magnetization plateau induced by single-ion anisotropy D is obtained in the model of the ferrimagnetic spin chain by using Dyson–Maleev mean-field theory.展开更多
To achieve a lower detection limit has always been a goal of analytical chemists.Herein,we demonstrate the first picomolar level detection capability for Fe3+ion via luminescence detection technology.The results of st...To achieve a lower detection limit has always been a goal of analytical chemists.Herein,we demonstrate the first picomolar level detection capability for Fe3+ion via luminescence detection technology.The results of structural analysis and theoretical calculation show that Fe3+ions are adsorbed on the central node of Eu-DBM(DBM=dibenzoylmethane)sensor in the form of single ion at ultralow concentration.Subsequently,the pathways of photo-induced charge and energy transfer of the obtained Eu-DBM@Fe^(3+)material have been changed,from the initial DBM-to-Eu^(3+)before Fe^(3+)adsorption to the ultimate DBM-to-Fe^(3+)after adsorption process,which quenches the luminescence of Eu3+ion.This work not only obtains the highly sensitive luminescence detection ability,but also innovatively proposes the single-ion adsorption mechanism,both of which have important scientific and application values for the development of more efficient detection agents in the future.展开更多
The application of solid polymer electrolytes(SPEs)is severely impeded by the insufficient ionic conductivity and low Li^(+)transference numbers(t_(Li)^(+)).Here,we report an iodine-driven strategy to address both the...The application of solid polymer electrolytes(SPEs)is severely impeded by the insufficient ionic conductivity and low Li^(+)transference numbers(t_(Li)^(+)).Here,we report an iodine-driven strategy to address both the two longstanding issues of SPEs simultaneously.Electronegative lodine-containing groups introduced on polymer chains effectively attract Li^(+)ions,facilitate Li^(+)transport,and promote the dissociation of Li salts.Meanwhile,iodine is also favorable to alleviate the strong O-Li^(+)coordination through a Lewis acidbase interaction,further improving the ionic conductivity and t_(Li)^(+).As a proof of concept,an iodinated single-ion conducting polymer electrolyte(IPE)demonstrates a high ionic conductivity of 0.93 mS cm^(-1)and a high t_(Li)^(+)of 0.86 at 25℃,which is among the best results ever reported for SPEs.Moreover,symmetric Li/Li cells with IPE achieve a long-term stability over 2600 h through the in-situ formed LiF-rich interphase.As a result,Li-S battery with IPE maintains a high capacity of 623.7 mAh g^(-1)over 300 cycles with an average Coulombic efficiency of 99%.When matched with intercalation cathode chemistries,Li/IPE/LiFePO_(4)and Li/IPE/LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)solid-state batteries also deliver high-capacity retentions of 95%and 97%at 0.2 C after 120 cycles,respectively.展开更多
Single-ion conducting polymer electrolytes(SIPEs)are promising candidates for high-energy and highsafety lithium-metal batteries(LMBs).However,their insufficient ionic conductivity and electrochemical stability hinder...Single-ion conducting polymer electrolytes(SIPEs)are promising candidates for high-energy and highsafety lithium-metal batteries(LMBs).However,their insufficient ionic conductivity and electrochemical stability hinder their practical application.Herein,three new SIPEs,i.e.,poly(1,4-phenylene ether ether sulfone)-Li(PEES-Li),polysulfone-Li(PSF-Li),and hexafluoropolysulfone-Li(6FPSF-Li),all containing covalently tethered perfluorinated ionic side chains,have been designed,synthesized,and compared to investigate the influence of the backbone chemistry and the concentration of the ionic group on their electrochemical properties and cell performance.Especially,the trifluoromethyl group in the backbone and the concentration of the ionic function appear to play an essential role for the charge transport and stability towards oxidation,and the combination of both yields the best-performing SIPE with high ionic conductivity of ca.2.5×10^(-4)S cm^(-1),anodic stability of more than 4.8 V,and the by far highest capacity retention in Li‖LiNi0.6Co0.2Mn0.2O2cells.展开更多
In this paper, the lowtemperature properties of the spin1 twodimensionM frustrated Heisenberg antifer romagnet with the singleion anisotropy are investigated on a square lattice by using the spinwave theory. The influ...In this paper, the lowtemperature properties of the spin1 twodimensionM frustrated Heisenberg antifer romagnet with the singleion anisotropy are investigated on a square lattice by using the spinwave theory. The influence of the frustration and anisotropy is found in the thermodynamics of the model, such as the temperature dependence of the staggered magnetization and specific heat. For some selected values of the frustration and anisotropy parameters, the results for the specific heat are compared with those of existing theories and numerical estimates. Within a spinwave analysis, we have found the evidence for an intermediate magnetically disorder phase to separate the Nel and collinear phases.展开更多
Within the framework of an effective field approximation, the effects of single-ion anisotropy and different trimodal transverse fields of two sublattices on the critical properties of the mixed spin-1/2 and spin-1 Is...Within the framework of an effective field approximation, the effects of single-ion anisotropy and different trimodal transverse fields of two sublattices on the critical properties of the mixed spin-1/2 and spin-1 Ising system are investigated on the simple cubic lattice. A smaller single-lon anisotropy can magnify magnetic ordering phases and a larger one can depress magnetic ordering phase for T-Ω1/2 space at low temperatures, while a smaller single-ion anisotropy can hardly change the value of critical transverse field for T-Ω1 space. On the other hand, influences of two different trimodal transverse fields concentrations on tricritical points and magnetic ordering phases take on some interesting results in T-D space. The main reason comes from the common action of single-ion anisotropy, different transverse fields and two trimodal distributions.展开更多
In the present paper, we investigate the quantum phase transition in a spatially anisotropic antiferrornagnetic Heisenberg model of S =1 with single-ion energy anisotropy. By using the Schwinger boson representation, ...In the present paper, we investigate the quantum phase transition in a spatially anisotropic antiferrornagnetic Heisenberg model of S =1 with single-ion energy anisotropy. By using the Schwinger boson representation, we calculate the Gaussian correction to the critical value J⊥^c caused by quantum spin fluctuations. We find that, for the positive single-ion energy, a nonzero value of J⊥^c is always needed to stabilize the antiferromagnetic long-range order in this model. It resolves a difference among literature and shows clearly that the effect of quantum fluctuations may qualitatively change a result obtained by the mean-field theories on lower-dimensional systems.展开更多
We study the ferrimagnetic properties of spin 1/2 and spin-1 systems by means of the effective field theory. The system is considered in the framework of bond dilution mixed Blume-Capel mode/ （BCM） with random singl...We study the ferrimagnetic properties of spin 1/2 and spin-1 systems by means of the effective field theory. The system is considered in the framework of bond dilution mixed Blume-Capel mode/ （BCM） with random single-ion anisotropy. The investigation of phase diagrams and magnetization curves indicates the existence of induced magnetic ordering and single or multi-compensation points. Special emphasis is placed on the influence of bond dilution and random single-ion anisotropy on normal or induced magnetic ordering states and single or multi-compensation points. Normal magnetic ordering states take on new phase diagrams with increasing randomness （bond and anisotropy）, while anisotropy induced magnetic ordering states are always occurrence no matter whether concentration of anisotropy is large or small. Existence and disappearance of compensation points rely strongly on bond dilution and random singleion anisotropy. Some results have not been revealed in previous papers and predicted by Néel theory of ferrimagnetism.展开更多
Single-ion conductors based on covalent organic frameworks(COFs)have garnered attention as a potential alternative to currently prevalent inorganic ion conductors owing to their structural uniqueness and chemical vers...Single-ion conductors based on covalent organic frameworks(COFs)have garnered attention as a potential alternative to currently prevalent inorganic ion conductors owing to their structural uniqueness and chemical versatility.However,the sluggish Li+conduction has hindered their practical applications.Here,we present a class of solvent-free COF single-ion conductors(Li-COF@P)based on weak ion-dipole interaction as opposed to traditional strong ion-ion interaction.The ion(Li+from the COF)-dipole(oxygen from poly(ethylene glycol)diacrylate embedded in the COF pores)interaction in the Li-COF@P promotes ion dissociation and Li+migration via directional ionic channels.Driven by this single-ion transport behavior,the Li-COF@P enables reversible Li plating/stripping on Li-metal electrodes and stable cycling performance(88.3%after 2000 cycles)in organic batteries(Li metal anode||5,5’-dimethyl-2,2’-bis-p-benzoquinone(Me2BBQ)cathode)under ambient operating conditions,highlighting the electrochemical viability of the Li-COF@P for all-solid-state organic batteries.展开更多
Poly(lithium propionate methyl siloxane )as a single-ion carrier source was synthesized. The crosslinked film showed lower lithium ionic conductivity at room temperature (about 10^(-10) S/cm). However,the lithium ioni...Poly(lithium propionate methyl siloxane )as a single-ion carrier source was synthesized. The crosslinked film showed lower lithium ionic conductivity at room temperature (about 10^(-10) S/cm). However,the lithium ionic conductivity was obviously increased by blending with high polar polymers such as polyethylene oxide, poly (methylsiloxane - co- ethylene oxide) and poly (methylsiloxane- g- ethylene oxide). In the blend system a high conductivity of 10^(-7)-10^(-5) Scm^(-1) at room temperature was obtained and the single-ion conductivity was deeply influenced by the content of the poly (lithium propionate methyl siioxane). The dc ionic conductivity of the flexible crosslinked films is more stable over time.展开更多
Cellular micro-irradiation is now recognized as a powerful technique to unveil the mechanisms of interaction between ionizing radiation and living cells or tissues. The single-ion microbeam （SIM） is uniquely capable...Cellular micro-irradiation is now recognized as a powerful technique to unveil the mechanisms of interaction between ionizing radiation and living cells or tissues. The single-ion microbeam （SIM） is uniquely capable of delivering precisely the predefined number of charged particles （precise doses of radiation） to specific individual cells or sub-cellular targets in situ. No active research in the field concerning the original process of the interaction between low-energy ions and complicated organisms has been reported yet. To address this challenge, the aim of the present design is to further wrestle with multi-dimensional quantitative information from living cells traversed by an exact number of ions real-time rather than endpoints, in the time scale from milliseconds to days.展开更多
Single-Ion Microbeam (SIM) is uniquely capable of precisely delivering a predefined number of charged particles (precise doses of radiation) to individual cells or sub-cellular targets in situ. Since the early 1990...Single-Ion Microbeam (SIM) is uniquely capable of precisely delivering a predefined number of charged particles (precise doses of radiation) to individual cells or sub-cellular targets in situ. Since the early 1990's, there has been an ever-increasing interest in developing and applying the SIM technique to problems in radiobiology for studies of cell and tissue damaged by ionizing radiations. Potential applications for SIM in radiobiology continues to grow and have been diversified. There are currently more than 14 SIM facilities worldwide, and they have been in a constant state of evolution. This paper reviews the current state of SIM research worldwide and the related pivotal technological developments in the fields of both biophysics and radiobiology. Representative applications and the perspective of SIM are also introduced and discussed.展开更多
We analytically investigate Multiple Quantum(MQ) NMR dynamics in a mixed-three-spin(1/2,1,1/2)system with XXX Heisenberg model at the front of an external homogeneous magnetic field B. A single-ion anisotropy property...We analytically investigate Multiple Quantum(MQ) NMR dynamics in a mixed-three-spin(1/2,1,1/2)system with XXX Heisenberg model at the front of an external homogeneous magnetic field B. A single-ion anisotropy property ζ is considered for the spin-1. The intensities dependence of MQ NMR coherences on their orders(zeroth and second orders) for two pairs of spins(1,1/2) and(1/2,1/2) of the favorite tripartite system are obtained. It is also investigated dynamics of the pairwise quantum entanglement for the bipartite(sub)systems(1,1/2) and(1/2,1/2)permanently coupled by, respectively, coupling constants J_1 and J_2, by means of concurrence and fidelity. Then, some straightforward comparisons are done between these quantities and the intensities of MQ NMR coherences and ultimately some interesting results are reported. We also show that the time evolution of MQ coherences based on the reduced density matrix of the pair spins(1,1/2) is closely connected with the dynamics of the pairwise entanglement. Finally, we prove that one can introduce MQ coherence of the zeroth order corresponds to the pair spins(1,1/2) as an entanglement witness at some special time intervals.展开更多
The low lithium transference number of conventional dual-ion polymer electrolytes will lead to concentration polarization and lithium dendrite growth,thereby affecting the safety and cycling performance of lithium bat...The low lithium transference number of conventional dual-ion polymer electrolytes will lead to concentration polarization and lithium dendrite growth,thereby affecting the safety and cycling performance of lithium batteries.Herein,we report a flame-retardant polycarbonate-based single-ion conducting polymer electrolyte(PAGEC-B/PFN).Due to the immobilization of anions within the polycarbonate crosslinking network,PAGEC-B/PFN exhibits a high lithium transference number(0.86),which is beneficial for alleviating concentration polarization and suppressing the growth of lithium dendrite.With the assistance of the TEP flame retardant and FEC,as well as LiNO_(3) additives,PAGEC-B/PFN exhibits excellent flame retardancy,high ionic conductivity,and outstanding interfacial compatibility with the lithium metal anode.As expected,PAGEC-B/PFN achieves a high critical current density of up to 2.0 mA cm^(-2)and stable cycling of Li‖Li cell for over 2200 h.Meanwhile,LFP‖PAGEC-B/PFN‖Li cell delivers a specific capacity of 147.8 mA h g^(-1)at 0.5 C and exhibits excellent cycling performance over 600 cycles.This work provides a strategy for designing solid-state lithium batteries with high safety and high performance.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos. 22075130 and 21875102)the Fundamental Research Funds for the Central Universities
文摘Solid-state electrolytes are considered to be the vital part of the next-generation solid-state batteries(SSBs),due to their high safety and long operation life span.However,the two major factors that impede the expected performance of batteries are:the easy formation of lithium dendrites due to the concentration gradient of anions,and the low ionic conductivity at room temperature,which prevents reaching ideal electrochemical performance.Single-ion quasi-solid-state electrolytes(SIQSSEs)could provide higher safety and energy density,owing to absence of anion concentration gradient and solvent,as well as good lithium-ion transport ability.The porous covalent organic frameworks(COFs)are beneficial for con-structing appropriate lithium-ion transport pathway,due to the ordered 1D channel.In addition,the boroxine COFs(COF-5)offers strong ability of withdrawing anion part of lithium salt.Last but not the least,boron atom could play the role of coordinate site due to its electron deficiency.These advantages afford an opportunity to obtain a SIQSSE with high ionic conductivity and high lithium transference number(LTN)simultaneously.The COF-5 based SIQSSEs delivered a high ionic conductivity of 6.3×10^(-4)S·cm^(-1),with a high LTN of 0.92 and a wide electrochemical stable window(ESW)of 4.7 V at room temperature.The LiFePO4(LFP)/Li cells,which was assembled with COF-5 based SIQSSE,exhibited outstanding long cycle stability,high initial capacity and favorable rate performance.The results indicated COFs could be an ideal material for single-ion solid-state electrolytes in next-generation batteries.
基金supported by the National Natural Science Foundation of China(52473206,U21A20330,52073118)the“111”Project(B18012l)+1 种基金the Shenzhen Science and Technology Plan Funding(JCYJ20230807112800001)the Open Research Funding of State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences(PPCL2024-016)。
文摘While single-ion conducting solid polymer electrolytes(SPE)offer inherent safety advantages for lithium metal batteries,their practical implementation is hindered by inadequate ionic transport and unstable electrode interfaces.We presented a breakthrough single-ion SPE system through molecular engineering of lithium-enriched porous aromatic frameworks(PAF-228-Li)integrated with poly(ethylene oxide),achieving exceptional ion conduction and interfacial stability.The precisely designed PAF-228-Li architecture established continuous 3D Li+transport pathways through its intrinsic porous channels and surface conduction sites,synergistically enhanced by PVDF-HFP nanofiber networks.This unique design enabled record-high ionic conductivities of 5.48×10^(-4)S cm^(-1)at 30℃and 3.4×10^(-4)S cm^(-1)at-20℃—among the best reported for PEO-based SPEs.The electrolyte spontaneously formed a selflimiting SEI rich in LiF/Li3N,effectively suppressing dendritic growth while enabling unprecedented cycling stability:Li||LiFePO4cells maintain 83.7%capacity over 700 cycles(30℃)and deliver 104.4 mA h g^(-1)after 1100 cycles at-20℃.Practical viability is further demonstrated in pouch cell configurations with stable operation at 30℃.This work pioneers a materials paradigm combining porous framework engineering with polymer electrolyte design,establishing new researching direction for low-temperature compatible,dendrite-resistant solid-state batteries.
基金supported by the National Natural Science Foundation of China(22179149,22075329,51573215,and 21978332)Research and Development Project of Henan Academy Sciences China(232018002)。
文摘Single ion gel polymer electrolyte has the advantages of high Li^(+)conductivity and dendrite mitigation.However,the addition of organic solvent makes the electrolyte flammable,posing serious safety hazards.Herein,we report a flame-retard ant cross-linked sp^(3)boron-based single-ion gel polymer electrolyte(BSIPE).BSIPE was prepared by a simple one-step photoinitiated in situ thiol-ene click reaction.Due to the boron-based anions being immobilized in the cross-linking network,the developed BSIPE/PFN exhibits a high t_(Li^(+))(0.87),which can mitigate concentration polarization phenomenon and suppress the growth of lithium dendrites.BSIPE/PFN plasticized with triethyl phosphate(TEP),fluoroethylene carbonate(FEC)and LiNO_(3)exhibits enhanced ionic conductivity of 4.25×10^(-4)S cm^(-1)at 30℃ and flame retardancy.FEC and LiNO_(3) are conducive to form a stable solid electrolyte interphase(SEI)rich in Li_(3)N and LiF to improve interface stability.As expected,the dendrite-free Li‖BSIPE/PFN‖Li symmetric cell exhibits considerable cycling life over 1500 h.BSIPE/PFN significantly boosts the performance of LFP‖Li cell,which displays a capacity retention of 84.6%after 500 cycles.The BSIPE/PFN has promising applications in highsafety and high-performance lithium metal batteries.
基金National Natural Science Foundation of China (No. 22209014)5.5 Engineering Research & Innovation Team Project of Beijing Forestry University (No.BLRC 2023B05)。
文摘The practical application of rechargeable lithium metal batteries(LMBs) encounters significant challenges due to the notorious dendrite growth triggered by uneven Li deposition behaviors. In this work,a mechanically robust and single-ion-conducting interfacial layer, fulfilled by the strategic integration of flexible cellulose acetate(CA) matrix with rigid graphene oxide(GO) and Li F fillers(termed the CGL layer), is rationally devised to serve as a stabilizer for dendrite-free lithium(Li) metal batteries. The GCL film exhibits favorable mechanical properties with high modulus and flexibility that help to relieve interface fluctuations. More crucially, the electron-donating carbonyl groups(C=O) enriched in GCL foster a strengthened correlation with Li^(+), which availably aids the Li^(+)desolvation process and expedites facile Li^(+)mobility, yielding exceptional Li^(+) transference number of 0.87. Such single-ion conductive properties regulate rapid and uniform interfacial transport kinetics, mitigating the growth of Li dendrites and the decomposition of electrolytes. Consequently, stable Li anode with prolonged cycle stabilities and flat deposition morphologies are realized. The Li||LiFePO_(4) full cells with CGL protective layer render an outstanding cycling capability of 500 cycles at 3 C, and an ultrahigh capacity retention of 99.99% for over 220 cycles even under harsh conditions. This work affords valuable insights into the interfacial regulation for achieving high-performance LMBs.
基金supported by the National Natural Science Foundation of China(51973157,51873152)Project funded by the China Postdoctoral Science Foundation(2022M711959)State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘With the depletion of fossil fuels and the demand for high-performance energy storage devices,solidstate lithium metal batteries have received widespread attention due to their high energy density and safety advantages.Among them,the earliest developed organic solid-state polymer electrolyte has a promising future due to its advantages such as good mechanical flexibility,but its poor ion transport performance dramatically limits its performance improvement.Therefore,single-ion conducting polymer electrolytes(SICPEs)with high lithium-ion transport number,capable of improving the concentration polarization and inhibiting the growth of lithium dendrites,have been proposed,which provide a new direction for the further development of high-performance organic polymer electrolytes.In view of this,lithium ions transport mechanisms and design principles in SICPEs are summarized and discussed in this paper.The modification principles currently used can be categorized into the following three types:enhancement of lithium salt anion-polymer interactions,weakening of lithium salt anion-cation interactions,and modulation of lithium ion-polymer interactions.In addition,the advances in single-ion conductors of conventional and novel polymer electrolytes are summarized,and several typical highperformance single-ion conductors are enumerated and analyzed in what way they improve ionic conductivity,lithium ions mobility,and the ability to inhibit lithium dendrites.Finally,the advantages and design methodology of SICPEs are summarized again and the future directions are outlined.
基金supported by the Fundamental Research Funds for Central Universities of China and the Key Research and Development Projects of Sichuan (No.2020YFG0127)。
文摘Lithium metal is deemed as an ideal anode material in lithium-ion batteries because of its ultrahigh theoretical specific capacity and the lowest redox potential.However,the rapid capacity attenuation and inferior security resulting from the dendritic lithium growth severely limit its commercialization.Herein a novel hybrid gel polymer electrolyte (GPE) based on electrospun lithium sulfonated polyoxadiazole (LiSPOD) nanofibrous membrane swelled by lithium bis(trifluoromethanesulfonyl)imide (Li TFSI) ether liquid electrolyte is proposed to address the issue of lithium dendrites.The Li-SPOD membrane synthesized by a simple one-pot method exhibits excellent mechanical strength and thermal resistance due to its high molecular weight and rigid backbone.The electron-withdrawing oxadiazole ring and oxadiazole ring-Li;complex,and N,O heteroatoms with lone pairs of electrons in Li-SPOD macromolecular chains facilitate the dissociation of-SO_(3)Li group and Li^(+)transference.The hybrid Li-SPOD GPE exhibits both a high lithium-ion transference number (0.64) and high ionic conductivity (2.03 m S/cm) as well as superior interfacial compacity with lithium anodes.The Li Fe PO_(4)-Li cell using this novel GPE can operate steadily at 2C for 300 cycles,remaining a high discharge capacity of 125 m Ah/g and dendrite-free anode.Remarkable performance improvements for the Li-Li and Cu-Li cells are also presented.
基金Project supported by the National Natural Science Foundation of China(Grant No.10774035)the Qianjiang RenCai Program of Zhejiang Province,China(Grant No.2007R0010)
文摘We use the mean-field approximation of Dyson–Maleev representation to study an XXZ Heisenberg ferrimagnetic spin chain with single-ion anisotropy. By solving the self-consistent equations with different anisotropies, λ and D respectively,the energy spectrums, internal energy, static susceptibility and specific heat are calculated. Especially, the quantum phase transition of the magnetization plateau induced by single-ion anisotropy D is obtained in the model of the ferrimagnetic spin chain by using Dyson–Maleev mean-field theory.
基金the National Natural Science Foundation of China(No.22075071)Harbin Manufacturing Science and Technology Innovation Talent Project(No.2022CXRCCG016)+1 种基金Outstanding Youth Science Foundation of Heilongjiang University(No.JCL202002)Special Project of Joint Dairy College in East University of Heilongjiang-National Dairy Engineering and Technology Research Center(No.LHXYDS202001).
文摘To achieve a lower detection limit has always been a goal of analytical chemists.Herein,we demonstrate the first picomolar level detection capability for Fe3+ion via luminescence detection technology.The results of structural analysis and theoretical calculation show that Fe3+ions are adsorbed on the central node of Eu-DBM(DBM=dibenzoylmethane)sensor in the form of single ion at ultralow concentration.Subsequently,the pathways of photo-induced charge and energy transfer of the obtained Eu-DBM@Fe^(3+)material have been changed,from the initial DBM-to-Eu^(3+)before Fe^(3+)adsorption to the ultimate DBM-to-Fe^(3+)after adsorption process,which quenches the luminescence of Eu3+ion.This work not only obtains the highly sensitive luminescence detection ability,but also innovatively proposes the single-ion adsorption mechanism,both of which have important scientific and application values for the development of more efficient detection agents in the future.
基金supported by the National Science Foundation of China(Grant No.5202780089)the Fundamental Research Funds for the Central Universities(HUST:2172020kfy XJJS089)the Open Research Fund of CNMGE Platform&NSCC-TJ(Grant No.CNMGE202101006)
文摘The application of solid polymer electrolytes(SPEs)is severely impeded by the insufficient ionic conductivity and low Li^(+)transference numbers(t_(Li)^(+)).Here,we report an iodine-driven strategy to address both the two longstanding issues of SPEs simultaneously.Electronegative lodine-containing groups introduced on polymer chains effectively attract Li^(+)ions,facilitate Li^(+)transport,and promote the dissociation of Li salts.Meanwhile,iodine is also favorable to alleviate the strong O-Li^(+)coordination through a Lewis acidbase interaction,further improving the ionic conductivity and t_(Li)^(+).As a proof of concept,an iodinated single-ion conducting polymer electrolyte(IPE)demonstrates a high ionic conductivity of 0.93 mS cm^(-1)and a high t_(Li)^(+)of 0.86 at 25℃,which is among the best results ever reported for SPEs.Moreover,symmetric Li/Li cells with IPE achieve a long-term stability over 2600 h through the in-situ formed LiF-rich interphase.As a result,Li-S battery with IPE maintains a high capacity of 623.7 mAh g^(-1)over 300 cycles with an average Coulombic efficiency of 99%.When matched with intercalation cathode chemistries,Li/IPE/LiFePO_(4)and Li/IPE/LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)solid-state batteries also deliver high-capacity retentions of 95%and 97%at 0.2 C after 120 cycles,respectively.
基金the financial support from the Federal Ministry of Education and Research(BMBF)within the Fest Batt project(03XP0175B)the FB2-Poly project(03XP0429B)the financial support from the Helmholtz Association。
文摘Single-ion conducting polymer electrolytes(SIPEs)are promising candidates for high-energy and highsafety lithium-metal batteries(LMBs).However,their insufficient ionic conductivity and electrochemical stability hinder their practical application.Herein,three new SIPEs,i.e.,poly(1,4-phenylene ether ether sulfone)-Li(PEES-Li),polysulfone-Li(PSF-Li),and hexafluoropolysulfone-Li(6FPSF-Li),all containing covalently tethered perfluorinated ionic side chains,have been designed,synthesized,and compared to investigate the influence of the backbone chemistry and the concentration of the ionic group on their electrochemical properties and cell performance.Especially,the trifluoromethyl group in the backbone and the concentration of the ionic function appear to play an essential role for the charge transport and stability towards oxidation,and the combination of both yields the best-performing SIPE with high ionic conductivity of ca.2.5×10^(-4)S cm^(-1),anodic stability of more than 4.8 V,and the by far highest capacity retention in Li‖LiNi0.6Co0.2Mn0.2O2cells.
文摘In this paper, the lowtemperature properties of the spin1 twodimensionM frustrated Heisenberg antifer romagnet with the singleion anisotropy are investigated on a square lattice by using the spinwave theory. The influence of the frustration and anisotropy is found in the thermodynamics of the model, such as the temperature dependence of the staggered magnetization and specific heat. For some selected values of the frustration and anisotropy parameters, the results for the specific heat are compared with those of existing theories and numerical estimates. Within a spinwave analysis, we have found the evidence for an intermediate magnetically disorder phase to separate the Nel and collinear phases.
基金The project supported partly by the Key Projects of Natural Science Foundation of Jiangsu Province of China under Grant No. 03KJA140117 and the 0pen Foundation of Jiangsu Key Laboratory of Thin Films under Grant No. K2022
文摘Within the framework of an effective field approximation, the effects of single-ion anisotropy and different trimodal transverse fields of two sublattices on the critical properties of the mixed spin-1/2 and spin-1 Ising system are investigated on the simple cubic lattice. A smaller single-lon anisotropy can magnify magnetic ordering phases and a larger one can depress magnetic ordering phase for T-Ω1/2 space at low temperatures, while a smaller single-ion anisotropy can hardly change the value of critical transverse field for T-Ω1 space. On the other hand, influences of two different trimodal transverse fields concentrations on tricritical points and magnetic ordering phases take on some interesting results in T-D space. The main reason comes from the common action of single-ion anisotropy, different transverse fields and two trimodal distributions.
基金The project partially supported by National Natural Science Foundation of China under Grant No. 90403003 We thank Prof. Xiao-Qun Wang and Prof. Tao Li for useful discussions. Numerical computation of this work was carried out on the Parallel Computer Cluster of Insti- tute for Condensed Matter Physics （ICMP） at School of Physics, Peking University.
文摘In the present paper, we investigate the quantum phase transition in a spatially anisotropic antiferrornagnetic Heisenberg model of S =1 with single-ion energy anisotropy. By using the Schwinger boson representation, we calculate the Gaussian correction to the critical value J⊥^c caused by quantum spin fluctuations. We find that, for the positive single-ion energy, a nonzero value of J⊥^c is always needed to stabilize the antiferromagnetic long-range order in this model. It resolves a difference among literature and shows clearly that the effect of quantum fluctuations may qualitatively change a result obtained by the mean-field theories on lower-dimensional systems.
文摘We study the ferrimagnetic properties of spin 1/2 and spin-1 systems by means of the effective field theory. The system is considered in the framework of bond dilution mixed Blume-Capel mode/ （BCM） with random single-ion anisotropy. The investigation of phase diagrams and magnetization curves indicates the existence of induced magnetic ordering and single or multi-compensation points. Special emphasis is placed on the influence of bond dilution and random single-ion anisotropy on normal or induced magnetic ordering states and single or multi-compensation points. Normal magnetic ordering states take on new phase diagrams with increasing randomness （bond and anisotropy）, while anisotropy induced magnetic ordering states are always occurrence no matter whether concentration of anisotropy is large or small. Existence and disappearance of compensation points rely strongly on bond dilution and random singleion anisotropy. Some results have not been revealed in previous papers and predicted by Néel theory of ferrimagnetism.
基金supported by the Basic Science Research Program (No.RS-2024-00344021) through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and future Planningthe financial support from the National Natural Science Foundation of China (52103277)+2 种基金the Program for Science & Technology Innovation Talents in Universities of Henan Province (23HASTIT015)Natural Science Foundation of Henan Province (242300421073)supported by the Technology Innovation Program (20010960) funded by the Ministry of Trade, Industry & Energy (MOTIE, Korea)
文摘Single-ion conductors based on covalent organic frameworks(COFs)have garnered attention as a potential alternative to currently prevalent inorganic ion conductors owing to their structural uniqueness and chemical versatility.However,the sluggish Li+conduction has hindered their practical applications.Here,we present a class of solvent-free COF single-ion conductors(Li-COF@P)based on weak ion-dipole interaction as opposed to traditional strong ion-ion interaction.The ion(Li+from the COF)-dipole(oxygen from poly(ethylene glycol)diacrylate embedded in the COF pores)interaction in the Li-COF@P promotes ion dissociation and Li+migration via directional ionic channels.Driven by this single-ion transport behavior,the Li-COF@P enables reversible Li plating/stripping on Li-metal electrodes and stable cycling performance(88.3%after 2000 cycles)in organic batteries(Li metal anode||5,5’-dimethyl-2,2’-bis-p-benzoquinone(Me2BBQ)cathode)under ambient operating conditions,highlighting the electrochemical viability of the Li-COF@P for all-solid-state organic batteries.
基金This work was supported by the National Natural Science Foundation of China
文摘Poly(lithium propionate methyl siloxane )as a single-ion carrier source was synthesized. The crosslinked film showed lower lithium ionic conductivity at room temperature (about 10^(-10) S/cm). However,the lithium ionic conductivity was obviously increased by blending with high polar polymers such as polyethylene oxide, poly (methylsiloxane - co- ethylene oxide) and poly (methylsiloxane- g- ethylene oxide). In the blend system a high conductivity of 10^(-7)-10^(-5) Scm^(-1) at room temperature was obtained and the single-ion conductivity was deeply influenced by the content of the poly (lithium propionate methyl siioxane). The dc ionic conductivity of the flexible crosslinked films is more stable over time.
基金the National Major Technologies R&D Program of China during the 10tb Five-Year Plan Period(No.2001BA30213)the National Science Fund for Distinguished Young Scholars(No.10225526)+1 种基金the Knowledge Innovation Program of the Chinese Academy of Sciences(No.KSCX2-SW-324)the Foundation for Key University Teachers by the Ministry of Education(No.2005jq1135)
文摘Cellular micro-irradiation is now recognized as a powerful technique to unveil the mechanisms of interaction between ionizing radiation and living cells or tissues. The single-ion microbeam （SIM） is uniquely capable of delivering precisely the predefined number of charged particles （precise doses of radiation） to specific individual cells or sub-cellular targets in situ. No active research in the field concerning the original process of the interaction between low-energy ions and complicated organisms has been reported yet. To address this challenge, the aim of the present design is to further wrestle with multi-dimensional quantitative information from living cells traversed by an exact number of ions real-time rather than endpoints, in the time scale from milliseconds to days.
基金The project supported by the National Major Technologies R & D Program of China during the 10th Five-Year Plan Period (No.2001BA302B)and the National Science Fund for Distinguished Young Scholars (No. 10225526)
文摘Single-Ion Microbeam (SIM) is uniquely capable of precisely delivering a predefined number of charged particles (precise doses of radiation) to individual cells or sub-cellular targets in situ. Since the early 1990's, there has been an ever-increasing interest in developing and applying the SIM technique to problems in radiobiology for studies of cell and tissue damaged by ionizing radiations. Potential applications for SIM in radiobiology continues to grow and have been diversified. There are currently more than 14 SIM facilities worldwide, and they have been in a constant state of evolution. This paper reviews the current state of SIM research worldwide and the related pivotal technological developments in the fields of both biophysics and radiobiology. Representative applications and the perspective of SIM are also introduced and discussed.
文摘We analytically investigate Multiple Quantum(MQ) NMR dynamics in a mixed-three-spin(1/2,1,1/2)system with XXX Heisenberg model at the front of an external homogeneous magnetic field B. A single-ion anisotropy property ζ is considered for the spin-1. The intensities dependence of MQ NMR coherences on their orders(zeroth and second orders) for two pairs of spins(1,1/2) and(1/2,1/2) of the favorite tripartite system are obtained. It is also investigated dynamics of the pairwise quantum entanglement for the bipartite(sub)systems(1,1/2) and(1/2,1/2)permanently coupled by, respectively, coupling constants J_1 and J_2, by means of concurrence and fidelity. Then, some straightforward comparisons are done between these quantities and the intensities of MQ NMR coherences and ultimately some interesting results are reported. We also show that the time evolution of MQ coherences based on the reduced density matrix of the pair spins(1,1/2) is closely connected with the dynamics of the pairwise entanglement. Finally, we prove that one can introduce MQ coherence of the zeroth order corresponds to the pair spins(1,1/2) as an entanglement witness at some special time intervals.
基金supported by the National Natural Science Foundation of China(22179149,22075329,51573215,and 21978332)Guangzhou Municipal Science and Technology Program(2025B01J2007,2025A03J4025,2025A03J4026)Fundamental Research Fund of Henan Academy of Sciences(232018002)。
文摘The low lithium transference number of conventional dual-ion polymer electrolytes will lead to concentration polarization and lithium dendrite growth,thereby affecting the safety and cycling performance of lithium batteries.Herein,we report a flame-retardant polycarbonate-based single-ion conducting polymer electrolyte(PAGEC-B/PFN).Due to the immobilization of anions within the polycarbonate crosslinking network,PAGEC-B/PFN exhibits a high lithium transference number(0.86),which is beneficial for alleviating concentration polarization and suppressing the growth of lithium dendrite.With the assistance of the TEP flame retardant and FEC,as well as LiNO_(3) additives,PAGEC-B/PFN exhibits excellent flame retardancy,high ionic conductivity,and outstanding interfacial compatibility with the lithium metal anode.As expected,PAGEC-B/PFN achieves a high critical current density of up to 2.0 mA cm^(-2)and stable cycling of Li‖Li cell for over 2200 h.Meanwhile,LFP‖PAGEC-B/PFN‖Li cell delivers a specific capacity of 147.8 mA h g^(-1)at 0.5 C and exhibits excellent cycling performance over 600 cycles.This work provides a strategy for designing solid-state lithium batteries with high safety and high performance.
