Lithium halide solid-state electrolytes,with the general formula of Li_(3±m)M_(n)X_(6),are regarded as the promising families of electrolyte material for all solid-state lithium-ion batteries because of the relat...Lithium halide solid-state electrolytes,with the general formula of Li_(3±m)M_(n)X_(6),are regarded as the promising families of electrolyte material for all solid-state lithium-ion batteries because of the relatively good ionic conductivity,high oxidative stability against high-voltage oxide cathodes,and broad electrochemical stability window[1].Here,M stands for one or multiple metal elements and X for one or multiple halogen elements.展开更多
Na_(5+x) YAl_x Si_(4-x) O_(12) polycrystalline solid electrolytes are prepared by solid reactions. By the analyses of X-ray, TG and DTA, infrared spectu re, and SEM, the variasion of their density with the composition...Na_(5+x) YAl_x Si_(4-x) O_(12) polycrystalline solid electrolytes are prepared by solid reactions. By the analyses of X-ray, TG and DTA, infrared spectu re, and SEM, the variasion of their density with the composition X are discussed Their electric conductivity in the temperature range of R. T. to 300℃ are determined with electric brigde, and their variasions with the compositions X and temperature are studied. Their activations in the tem- perature range 140℃ to 300℃ are calculated, and their variation with the compositons X are discussed.展开更多
The polyanionic material sodium vanadium phosphate(Na_(3)V_(2)(PO_(4))_(3),N_(3)VP)exhibits cost advantages and promising development prospects as a cathode material in sodium-ion batteries,an attractive safer alterna...The polyanionic material sodium vanadium phosphate(Na_(3)V_(2)(PO_(4))_(3),N_(3)VP)exhibits cost advantages and promising development prospects as a cathode material in sodium-ion batteries,an attractive safer alternative to lithium-ion batteries.However,suffering from intrinsically low electronic conductivity,optimizable ion diffusivity,and suboptimal structural stability N3VP cathode materials are still far from commercialization.展开更多
In the realm of lithium superionic conductors,pursuing higher ionic conductivity is imperative,with the variance in lithium-ion concentration playing a determining role.Due to the permanent and temporary site-blocking...In the realm of lithium superionic conductors,pursuing higher ionic conductivity is imperative,with the variance in lithium-ion concentration playing a determining role.Due to the permanent and temporary site-blocking effects,especially at non-dilute concentrations,not all Li-ions contribute to ionic conductivity.Here,we propose a strategy to directly calculate effective mobile ion concentration in which multiple-ion correlated migration is considered in the percolation analysis with the input of Li-ion distributions and hopping behavior based on kinetic Monte Carlo simulation,termed P-KMC.We provide examples of two representative lithium superionic conductors,cubic garnet-type LixA3B2O12(0≤x≤9;A and B represent different cations)and perovskite-type LixLa2/3−x/3TiO3(0≤x≤0.5),to demonstrate the direct dependence of the ionic conductivity on the effective mobile ion concentration.This methodology provides a robust tool to identify the optimal compositions for the highest ionic conductivity in superionic conductors.展开更多
Sodium-ion batteries(SIBs)have developed rapidly owing to the high natural abundance,wide distribution,and low cost of sodium.Among the various materials used in SIBs,sodium superion conductor(NASICON)-based electrode...Sodium-ion batteries(SIBs)have developed rapidly owing to the high natural abundance,wide distribution,and low cost of sodium.Among the various materials used in SIBs,sodium superion conductor(NASICON)-based electrode materials with remarkable structural stability and high ionic conductivity are one of the most promising candidates for sodium storage electrodes.Nevertheless,the relatively low electronic conductivity of these materials makes them display poor electrochemical performance,significantly limiting their practical application.In recent years,the strategies of enhancing the inherent conductivity of NASICON-based cathode materials have been extensively studied through coating the active material with a conductive carbon layer,reducing the size of the cathode material,combining the cathode material with various carbon materials,and doping elements in the bulk phase.In this paper,we review the recent progress in the development of NASICON-based cathode materials for SIBs in terms of their synthesis,characterization,functional mechanisms,and performance validation/optimization.The advantages and disadvantages of such SIB cathode materials are analyzed,and the relationship between electrode structures and electrochemical performance as well as the strategies for enhancing their electrical conductivity and structural stability is highlighted.Some technical challenges of NASICON-based cathode materials with respect to SIB performance are analyzed,and several future research directions are also proposed for overcoming the challenges toward practical applications.展开更多
As a novel class of porous crystalline solids,covalent organic frameworks(COFs)based electrolyte can combine the advantages of both inorganic and polymer electrolytes,leading to such as higher structural stability to ...As a novel class of porous crystalline solids,covalent organic frameworks(COFs)based electrolyte can combine the advantages of both inorganic and polymer electrolytes,leading to such as higher structural stability to inhibit lithium dendrites and better processing facility for improving interfacial contact.However,the ionic components of Li salt tend to be closely associated in the form of ion pairs or even ionic aggregates in the channel of COFs due to strong coulombic interactions,thus resulting in slow ionic diffusion dynamics and low ionic conductivity.Herein,we successfully designed and synthesized a novel single-ion conducting nitrogen hybrid conjugated skeleton(NCS)as all solid electrolyte,whose backbone is consisted with triazine and piperazine rings.A loose bonding between the triazine rings and cations would lower the energy barrier during ions transfer,and electrostatic forces with piperazine rings could“anchor”anions to increase the selectivity during ions transfer.Thus,the NCSelectrolyte exhibits excellent room temperature lithium-ion conductivity up to 1.49 mS·cm−1 and high transference number of 0.84 without employing any solvent,which to the best of our knowledge is one of the highest COF-based electrolytes so far.Moreover,the fabricated all-solid-state lithium metal batteries demonstrate highly attractive properties with quite stable cycling performance over 100 cycles with 82%capacity reservation at 0.5 C.展开更多
Rare-earth(RE)halide solid electrolytes(HSEs)have been an emerging research area due to their good electrochemical and mechanical properties for all-solid-state lithium batteries(ASSBs).However,only very limited types...Rare-earth(RE)halide solid electrolytes(HSEs)have been an emerging research area due to their good electrochemical and mechanical properties for all-solid-state lithium batteries(ASSBs).However,only very limited types of HSEs have been reported with high performance.In this work,tens of grams of RE-HSE Li_(3)TbBr_(6)(LTbB)was synthesized by a vacuum evaporationassisted method.The as-prepared LTbB displays a high ionic conductivity of 1.7 mS·cm^(-1),a wide electrochemical window,and good formability.Accordingly,the assembled solid lithium-tellurium(Li-Te)battery based on the LTbB HSE exhibits excellent cycling stability up to 600 cycles,which is superior to most previous reports.The processes and the chemicals during the discharge/charge of Li-Te batteries have been studied by various in situ and ex situ characterizations.Theoretical calculations have demonstrated the dominant conductivity contributions of the direct[octahedral]-[octahedral]([Oct]-[Oct])pathway for Li ion migrations in the electrolyte.The Tb sites guarantee efficient electron transfer while the Li 2s orbitals are not affected during migration,leading to a low activation barrier.Therefore,this successful fabrication and application of LTbB have offered a highly competitive solution for solid electrolytes in ASSBs,indicating the great potential of RE-based HSEs in energy devices.展开更多
Composition regulation of semiconductors can engineer their bandgaps and hence tune their properties.Herein,we report the first synthesis of ternary ZnxCd1-xS semiconductor nanorods by superionic conductor(AgRS)-media...Composition regulation of semiconductors can engineer their bandgaps and hence tune their properties.Herein,we report the first synthesis of ternary ZnxCd1-xS semiconductor nanorods by superionic conductor(AgRS)-mediated growth with[(C4H9)2NCS2]2M(M=Zn,ca)as single-source precursors.The compositions of the ZnKCd1-xS nanorods are conveniently tuned over a wide range by adjusting the molar ratio of the corresponding precursors,leading to tunable bandgaps and hence the progressive evolution of the light absorption and photoluminescence spectra.The nanorods present well-distributed size and length,which are controlled by the uniform Ag2S nanoparticles and the fixed amount of the precursors.The results suggest the great potential of superionic conductor-mediated growth in composition regulation and bandgap engineering of chalcogenide nanowires/nanorods.展开更多
Superionic conductors(SCs)exhibiting low ion migration activation energy(Ea)are critical to the performance of electrochemical energy storage devices such as solid-state batteries and fuel cells.However,it is challeng...Superionic conductors(SCs)exhibiting low ion migration activation energy(Ea)are critical to the performance of electrochemical energy storage devices such as solid-state batteries and fuel cells.However,it is challenging to obtain Ea experimentally and theoretically,and the artificial intelligence(AI)method is expected to bring a breakthrough in predicting Ea.Here,we proposed an AI platform(named AI-IMAE)to predict the Ea of cation and anion conductors,including Li^(+),Na^(+),Ag^(+),Al^(3+),Mg^(2+),Zn^(2+),Cu^((2)+),F^(−),and O^(2−),which is~105 times faster than traditional methods.The proposed AI-IMAE is based on crystal graph neural network models and achieves a holistic average absolute error of 0.19 eV,a median absolute error of 0.09 eV,and a Pearson coefficient of 0.92.Using AI-IMAE,we rapidly discovered 316 promising SCs as solid-state electrolytes and 129 SCs as cathode materials from 144,595 inorganic compounds.AI-IMAE is expected to completely solve the challenge of time-consuming Ea prediction and blaze a new trail for large-scale studies of SCs with excellent performance.As more experimental and high-precision theoretical data become available,AI-IMAE can train custom models and transfer the existing models to new models through transfer learning to constantly meet more demands.展开更多
The practical application of Na metal batteries is severely hindered by uncontrolled Na dendrite growth and large volume fluctuations,which lead to safety hazards and poor cycling stability.Herein,we designed a compos...The practical application of Na metal batteries is severely hindered by uncontrolled Na dendrite growth and large volume fluctuations,which lead to safety hazards and poor cycling stability.Herein,we designed a composite 3D Ni foam skeleton modified with fast-ion conductor(FIC)networks to achieve dual ionic/electronic conductivity,enabling spatially guided Na^(+)deposition and confined growth.The FIC modification exhibits strong Na+affinity,which ensures uniform ion distribution and directs Na^(+)deposition preferentially within the porous Ni framework rather than on its surface.This unique structure facilitates region-induced deposition and spatial confinement of Na metal,effectively suppressing dendrite formation and mitigating volume expansion.Moreover,the FIC network significantly enhances Na+transport kinetics during plating/stripping processes,improving electrochemical reversibility.As a result,the FIC-modified 3D Ni host provides stable Na metal anodes with a prolonged cycling life and reduced polarization.The symmetric cells exhibit stable operation for 300 hours at 0.5 mA cm^(−2)and 2 mAh cm^(−2),while full cells demonstrate an outstanding capacity retention of 94.6%at 5C over 400 cycles.This work presents a rational electrode design strategy that combines guided ion redistribution and physical confinement to achieve dendrite-free Na metal anodes,providing new insights for developing high energy density Na-based batteries.展开更多
Li-argyrodites are promising solid electrolytes(SEs)for solid-state Li-ion batteries(SSLBs),but their large-scale industrial application remains a challenge.Conventional synthesis methods for SEs suffer from long reac...Li-argyrodites are promising solid electrolytes(SEs)for solid-state Li-ion batteries(SSLBs),but their large-scale industrial application remains a challenge.Conventional synthesis methods for SEs suffer from long reaction times and high energy consumption.In this study,we present a wet process for the synthesis of halogen-rich argyrodite Li_(6-a)PS_(5-a)Cl_(1+a)precursors(LPSCl_(1+a)-P,a=0–0.7)via an energysaving microwave-assisted process.Utilizing vibrational heating,we accelerate the formation of Liargyrodite precursor,even at excessive Cl-ion concentration,which significantly shortens the reaction time compared to traditional methods.After crystallization,we successfully synthesize the Liargyrodite,Li_(5.5)PS_(4.5)Cl_(1.5),which exhibits the superior ionic conductivity(7.8 mS cm^(-1))and low activation energy(0.23 eV)along with extremely low electric conductivity.The Li_(5.5)PS_(4.5)Cl_(1.5)exhibits superior Li compatibility owing to its high reversible striping/plating ability(over 5000 h)and high current density acceptability(1.3 mA cm^(-2)).It also exhibits excellent cycle reversibility and rate capability with NCM622 cathode(148.3 mA h g^(-1)at 1 C for 100 cycles with capacity retention of 85.6%).This finding suggests a potentially simpler and more scalable synthetic route to produce high-performance SEs.展开更多
Consideringα-RbCu_(4)Cl_(3)I_(2)is isostructural withα-RbAg4I5,in this work,we built a molecular dynamics simulation system of the former superionic conductor with an empirical pairwise potential model,which was ver...Consideringα-RbCu_(4)Cl_(3)I_(2)is isostructural withα-RbAg4I5,in this work,we built a molecular dynamics simulation system of the former superionic conductor with an empirical pairwise potential model,which was verified on the latter crystal,including long-ranging Coulomb,short-ranging Born-Mayer,charge-dipole,and dipole-quadrupole interactions.The corresponding parameters were collected from the crystal structure and several reports of interionic potentials in alkali halides.The coordination number of fixed ions was examined,and the dynamic distribution of dissociative Cu+was described by the radial distribution function.The diffusion behavior of the ions was evaluated with mean square displacements and velocity auto-correlation functions.The diffusion coefficient of copper ions obtained is(47.9±6.1)×10-7cm^(2)/s,which is approximately 37 times that of the simulation result(1.3±0.1)×10^(-7)cm^(2)/s of silver inα-RbAg4I5at room temperature.In this work,the diffusion coefficient of Cu+was first discussed by molecule simulation,while there are few experimental reports.展开更多
Based on the excellent sodium ion mobility of sodium superionic conductor structures,Na_(3)V_(2)(PO_(4))_(3)materials have become promising cathode materials in sodium-ion batteries(SIBs).However,inadequate electronic...Based on the excellent sodium ion mobility of sodium superionic conductor structures,Na_(3)V_(2)(PO_(4))_(3)materials have become promising cathode materials in sodium-ion batteries(SIBs).However,inadequate electronic transport of Na_(3)V_(2)(PO_(4))_(3)limits the cycling stability and rate performances in SIBs.In this work,high-performance conductive carbon-coated Na_(3)V_(2)(PO_(4))_(3)materials are obtained via a simple and facile ball-milling assisted solid-state method by utilizing citric acid as carbon sources.The carbon-coated composite electrodes display a high initial specific capacity of 111.6 mAh·g^(-1),and the specific capacity could retention reach 92.83%after 100 cycles at 1C with the high coulombic efficiency(99.95%).More importantly,the capacity of conductive carbon-coated nano-sized Na_(3)V_(2)(PO_(4))_(3)can remain 48.5 mAh·g^(-1) at 10℃after 3000 cycles(initial capacity of 101.2 mAh·g^(-1)).At the same time,high coulombic efficiency(near 100%)has little decay even at a high rate of 20℃during 1000 cycles,demonstrating the excellent cycling stability and remarkable rate performances,and showing potential in largescale productions and applications.展开更多
Copper sulfide Cu2S is a p-type semiconducting compound that has attracted great attentions in the thermoelectric （TE） community most recently. Considering the intrinsic ultralow lattice thermal conductivity, the en...Copper sulfide Cu2S is a p-type semiconducting compound that has attracted great attentions in the thermoelectric （TE） community most recently. Considering the intrinsic ultralow lattice thermal conductivity, the enhancement of TE performance in CuzS should be achieved through improving its electrical transport properties. To achieve this goal, lithium element was doped into CuzS in this study. A series of Cu2_xLixS samples with different Li contents （x = 0, 0.005, 0.010, 0.050, and 0.100） was synthesized by the melting-annealing method. When x 〈 0.05, the Cuz_xLixS samples are stable and pure phases, having the same monoclinic structure with the pristine Cu2S at room temperature. The electrical conductivities in the Cu2_xLixS samples are greatly improved with the Li-doping content increasing due to the enhanced carrier concentrations. Meanwhile, doping Li into CuzS increases the ionic activation energy and lessens the influence of mobile Cu ions on the heat-carrying phonons. Thus, the thermal conductivities of the Li-doped Cu2S samples increase. A maximal figure of merit （zT） of 0.84 at 900 K is obtained in Cul.99Lio.018, about 133% improvement as compared with that in Cu2S matrix.展开更多
Rechargeable batteries based on solid-state electrolytes are of great interest and importance for the next-generation energy storage due to their high energy output and improved safety.For building the solid-state bat...Rechargeable batteries based on solid-state electrolytes are of great interest and importance for the next-generation energy storage due to their high energy output and improved safety.For building the solid-state batteries,Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)represents a promising candidate as it features high chemical stability against air exposure and a high Na^(+)conductivity.NZSP pellets were usually calcined at a high temperature,and the high volatility of Na and P elements easily led to the formation of impurity phase.In this work,the effects of calcination temperature and stoichiometry on the phase purity and ionic conductivity of the NZSP electrolyte were studied.At an elevated sintering temperature,the NZSP electrolyte showed a high ionic conductivity owing to decreased porosity,and the highest ionic conductivity at 30℃was observed to be 2.75×10^(-5)S·cm^(-1)with an activation energy of 0.41 eV.For the stoichiometry,the introduction of 5 mol%excessive P results in formation of more Na_(3)PO_(4) and glass-like phase at the grain boundary,which caused the blurred grain boundary and reduced grain barrier,and effectively suppressed Na dendrite growth,then accounted for improved cycling performance of a Na‖Na symmetric cell.Our work provided insights on reasonable design and preparation of NZSP electrolyte towards practical realization of solid-state Na-metal batteries.展开更多
Cu-and Ag-based superionic conductors are promising thermoelectric materials due to their good electrical properties and intrinsically low thermal conductivity. However, the poor electrical and thermal stability restr...Cu-and Ag-based superionic conductors are promising thermoelectric materials due to their good electrical properties and intrinsically low thermal conductivity. However, the poor electrical and thermal stability restrict their application. In this work, n-type pure phase Ag_(2) Te compound is synthesized by simply grinding elemental powders at room temperature and compacted by spark plasma sintering. It is found that, because of the migration of Ag+after the phase transition around 425 K, submicron pores are formed inside the samples during the electrical performance measurement, resulting in poor electrical stability and repeatability of Ag_(2) Te samples. However, Pb-doped Ag_(2-x)Pb_(x)Te(x = 0–0.05) specimens exhibit improved electrical stability by the precipitation of the secondary phase Pb Te in the Ag_(2) Te matrix, which is confirmed via cyclic electrical property measurement and microstructure characterization.A maximum z T = 0.72 is obtained at 570 K for x = 0.03 mainly due to the increased power factor.展开更多
Na superionic conductor（NASICON） nanoparticles were synthesized by a modified sol-gel method and sintered at a temperature range of 800--1000℃. The performance of the samples was characterized by the analysis metho...Na superionic conductor（NASICON） nanoparticles were synthesized by a modified sol-gel method and sintered at a temperature range of 800--1000℃. The performance of the samples was characterized by the analysis methods of X-ray diffraction（XRD）, Fourier transform infrared spectroscopy（FTIR）, and transmission electron microscopy（TEM） as well as conductivity measurement. Compared with those sintered at other temperatures, the NASICON material sintered at 900 ℃ had the best crystalline structure and higher conductivity.展开更多
The sharp decline in ionic conductivity at the liquid-solid phase transition is an intrinsic limitation of organic electrolytes.In conventional organic electrolytes(COEs),crystallization triggers pronounced conductivi...The sharp decline in ionic conductivity at the liquid-solid phase transition is an intrinsic limitation of organic electrolytes.In conventional organic electrolytes(COEs),crystallization triggers pronounced conductivity loss and deviates from Arrhenius behavior,reflecting a fundamental shift in ion-transport mechanisms(Figure 1a)[1,2].In contrast,inorganic superionic conductors sustain fast ion transport in crystalline lattices when migration barriers are low and diffusion sites are energetically comparable[3,4].展开更多
As an ion conductor, the Al-doped Li1+xAlxGe2-x(PO4)3(LAGP) demonstrates the superionic Li diffusion behavior, however,without the convinced verifications. In this context, the density functional theory(DFT) calculati...As an ion conductor, the Al-doped Li1+xAlxGe2-x(PO4)3(LAGP) demonstrates the superionic Li diffusion behavior, however,without the convinced verifications. In this context, the density functional theory(DFT) calculations are employed to clarify the structural origin of the fast Li ion migration kinetics in LAGP solid electrolytes. The calculated results show that doping of Al leads to an emerging high-energy 36 f Li site, which plays an important role in promoting the Li diffusion and can largely lower the Li ion diffusion energy barrier. Moreover, the Li/Al antisite defect is investigated firstly, with which the Li ions are excited to occupy a relatively high energy site in LAGP. The obvious local structural distortion by Li/Al antisite results in the coordination change upon Li diffusion(lattice field distortion), which facilitates the Li diffusion significantly and is probably the main reason to account for the superionic diffusion phenomenon. Therefore, the occupation of Li at high-energy sites should be an effective method to establish the fast Li diffusion, which implies a rewarding avenue to build better Li-ion batteries.展开更多
Recent discoveries in the antiperovskite-class sodium superionic conductors call for a thorough mole cular dynamics(MD)study of sodium ion mobility,but the practical use of MD is often hindered by the accuracy-vs.-eff...Recent discoveries in the antiperovskite-class sodium superionic conductors call for a thorough mole cular dynamics(MD)study of sodium ion mobility,but the practical use of MD is often hindered by the accuracy-vs.-effciency dilemma.Here we applied the recently developed deep potential molecular dynamics(DeePMD)approach to investigate the ion mobility in Na_(3)OBr.With the deep potential model for Na_(3)OBr constructed based onfirst-principles density-functional theory(DFT)calculations,we directly calculate the Na+diffusion coeffcient at various temperatures,and obtain an activation energy of 0.42-0.43 eV.This in comparison with the 0 K migration barrier(0.41-0.43 eV)suggests that thefinite temperature effect is negligible for Na_(3)OBr.The model gives an extrapolated room temperature ionic conductivity of 1×10^(−4)-2×10^(−4)mS cm^(−1),roughly in the same order of magnitude as the experimental results.We also confirm the proportionality of the diffusion coeffcient with respect to the vacancy con centration,andfind that the migration barrier is relatively insensitive to the vacancy concentration.This work further demonstrates the promising role of the DeePMD method in the study of the transport pro perties of solid-state electrolytes.展开更多
文摘Lithium halide solid-state electrolytes,with the general formula of Li_(3±m)M_(n)X_(6),are regarded as the promising families of electrolyte material for all solid-state lithium-ion batteries because of the relatively good ionic conductivity,high oxidative stability against high-voltage oxide cathodes,and broad electrochemical stability window[1].Here,M stands for one or multiple metal elements and X for one or multiple halogen elements.
文摘Na_(5+x) YAl_x Si_(4-x) O_(12) polycrystalline solid electrolytes are prepared by solid reactions. By the analyses of X-ray, TG and DTA, infrared spectu re, and SEM, the variasion of their density with the composition X are discussed Their electric conductivity in the temperature range of R. T. to 300℃ are determined with electric brigde, and their variasions with the compositions X and temperature are studied. Their activations in the tem- perature range 140℃ to 300℃ are calculated, and their variation with the compositons X are discussed.
基金supported by the National Natural Science Foundation of China[no.U21A20332,52103226,52202275,52203314,and 12204253]Postdoctoral Fellowship Program of CPSF under grant number GZC20231879the Distinguished Young Scholars Fund of Jiangsu Province[no.BK20220061].
文摘The polyanionic material sodium vanadium phosphate(Na_(3)V_(2)(PO_(4))_(3),N_(3)VP)exhibits cost advantages and promising development prospects as a cathode material in sodium-ion batteries,an attractive safer alternative to lithium-ion batteries.However,suffering from intrinsically low electronic conductivity,optimizable ion diffusivity,and suboptimal structural stability N3VP cathode materials are still far from commercialization.
基金supported by the National Natural Science Foundation of China(Nos.92270124,52102313,92472207)the Hunan Provincial Natural Science Foundation of China(No.2023JJ40635)+1 种基金Shandong Province Natural Science Foundation(No.ZR2022ZD11)the High-Performance Computing Center of Shanghai University and Shanghai Engineering Research Center of Intelligent Computing Systems for providing computing resources and technical support.
文摘In the realm of lithium superionic conductors,pursuing higher ionic conductivity is imperative,with the variance in lithium-ion concentration playing a determining role.Due to the permanent and temporary site-blocking effects,especially at non-dilute concentrations,not all Li-ions contribute to ionic conductivity.Here,we propose a strategy to directly calculate effective mobile ion concentration in which multiple-ion correlated migration is considered in the percolation analysis with the input of Li-ion distributions and hopping behavior based on kinetic Monte Carlo simulation,termed P-KMC.We provide examples of two representative lithium superionic conductors,cubic garnet-type LixA3B2O12(0≤x≤9;A and B represent different cations)and perovskite-type LixLa2/3−x/3TiO3(0≤x≤0.5),to demonstrate the direct dependence of the ionic conductivity on the effective mobile ion concentration.This methodology provides a robust tool to identify the optimal compositions for the highest ionic conductivity in superionic conductors.
基金the National Natural Science Foundation of China(Nos.51602193,21601122,21905169)the Belt and Road Initiatives International Cooperation Project(No.20640770300)+5 种基金the Shanghai“Chen Guang”Project(16CG63)the Shanghai Local Universities Capacity Building Project of Science and Technology Innovation Action Program(21010501700)the Shanghai Sailing Program(No.18YF1408600)the Fundamental Research Funds for the Central Universities(WD1817002)the EPSRC(EP/R023581/1,EP/P009050/1,EP/V027433/1)the Royal Society(RGS/R1/211080).
文摘Sodium-ion batteries(SIBs)have developed rapidly owing to the high natural abundance,wide distribution,and low cost of sodium.Among the various materials used in SIBs,sodium superion conductor(NASICON)-based electrode materials with remarkable structural stability and high ionic conductivity are one of the most promising candidates for sodium storage electrodes.Nevertheless,the relatively low electronic conductivity of these materials makes them display poor electrochemical performance,significantly limiting their practical application.In recent years,the strategies of enhancing the inherent conductivity of NASICON-based cathode materials have been extensively studied through coating the active material with a conductive carbon layer,reducing the size of the cathode material,combining the cathode material with various carbon materials,and doping elements in the bulk phase.In this paper,we review the recent progress in the development of NASICON-based cathode materials for SIBs in terms of their synthesis,characterization,functional mechanisms,and performance validation/optimization.The advantages and disadvantages of such SIB cathode materials are analyzed,and the relationship between electrode structures and electrochemical performance as well as the strategies for enhancing their electrical conductivity and structural stability is highlighted.Some technical challenges of NASICON-based cathode materials with respect to SIB performance are analyzed,and several future research directions are also proposed for overcoming the challenges toward practical applications.
基金We thank the financial support from the Natural Science Foundation of Shandong(Nos.ZR2020JQ21 and ZR2021ZD24)National Natural Science Foundation of China(Nos.51873231 and 22138013)+1 种基金Taishan Scholar Project(No.tsqn201909062)the Technology Foundation of Shandong Energy Group Co.,LTD.(YKZB2020-176,YKKJ2019AJ08JG-R63)。
文摘As a novel class of porous crystalline solids,covalent organic frameworks(COFs)based electrolyte can combine the advantages of both inorganic and polymer electrolytes,leading to such as higher structural stability to inhibit lithium dendrites and better processing facility for improving interfacial contact.However,the ionic components of Li salt tend to be closely associated in the form of ion pairs or even ionic aggregates in the channel of COFs due to strong coulombic interactions,thus resulting in slow ionic diffusion dynamics and low ionic conductivity.Herein,we successfully designed and synthesized a novel single-ion conducting nitrogen hybrid conjugated skeleton(NCS)as all solid electrolyte,whose backbone is consisted with triazine and piperazine rings.A loose bonding between the triazine rings and cations would lower the energy barrier during ions transfer,and electrostatic forces with piperazine rings could“anchor”anions to increase the selectivity during ions transfer.Thus,the NCSelectrolyte exhibits excellent room temperature lithium-ion conductivity up to 1.49 mS·cm−1 and high transference number of 0.84 without employing any solvent,which to the best of our knowledge is one of the highest COF-based electrolytes so far.Moreover,the fabricated all-solid-state lithium metal batteries demonstrate highly attractive properties with quite stable cycling performance over 100 cycles with 82%capacity reservation at 0.5 C.
基金This work was supported by the National Key R&D Program of China(No.2021YFA1501101)the Natural Science Foundation of China(No.21971117)+11 种基金Functional Research Funds for the Central Universities,Nankai University(No.63186005)Tianjin Key Lab for Rare Earth Materials and Applications(No.ZB19500202)the National Natural Science Foundation of China/Research Grant Council Joint Research Scheme(No.N_PolyU502/21)111 Project(No.B18030)from ChinaOutstanding Youth Project of Tianjin Natural Science Foundation(No.20JCJQJC00130)Key Project of Tianjin Natural Science Foundation(No.20JCZDJC00650)the Projects of Strategic Importance of The Hong Kong Polytechnic University(No.1-ZE2V)Shenzhen Fundamental Research Scheme-General Program(No.JCYJ20220531090807017)National Postdoctoral Program for Innovative Talents(No.BX20220157)Open Foundation of State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures(No.2022GXYSOF07)Haihe Laboratory of Sustainable Chemical Transformations.B.L.H.also thanks the support from Research Centre for Carbon-Strategic Catalysis(RCCSC),Research Institute for Smart Energy(RISE)Research Institute for Intelligent Wearable Systems(RI-IWEAR)of the Hong Kong Polytechnic University.
文摘Rare-earth(RE)halide solid electrolytes(HSEs)have been an emerging research area due to their good electrochemical and mechanical properties for all-solid-state lithium batteries(ASSBs).However,only very limited types of HSEs have been reported with high performance.In this work,tens of grams of RE-HSE Li_(3)TbBr_(6)(LTbB)was synthesized by a vacuum evaporationassisted method.The as-prepared LTbB displays a high ionic conductivity of 1.7 mS·cm^(-1),a wide electrochemical window,and good formability.Accordingly,the assembled solid lithium-tellurium(Li-Te)battery based on the LTbB HSE exhibits excellent cycling stability up to 600 cycles,which is superior to most previous reports.The processes and the chemicals during the discharge/charge of Li-Te batteries have been studied by various in situ and ex situ characterizations.Theoretical calculations have demonstrated the dominant conductivity contributions of the direct[octahedral]-[octahedral]([Oct]-[Oct])pathway for Li ion migrations in the electrolyte.The Tb sites guarantee efficient electron transfer while the Li 2s orbitals are not affected during migration,leading to a low activation barrier.Therefore,this successful fabrication and application of LTbB have offered a highly competitive solution for solid electrolytes in ASSBs,indicating the great potential of RE-based HSEs in energy devices.
文摘Composition regulation of semiconductors can engineer their bandgaps and hence tune their properties.Herein,we report the first synthesis of ternary ZnxCd1-xS semiconductor nanorods by superionic conductor(AgRS)-mediated growth with[(C4H9)2NCS2]2M(M=Zn,ca)as single-source precursors.The compositions of the ZnKCd1-xS nanorods are conveniently tuned over a wide range by adjusting the molar ratio of the corresponding precursors,leading to tunable bandgaps and hence the progressive evolution of the light absorption and photoluminescence spectra.The nanorods present well-distributed size and length,which are controlled by the uniform Ag2S nanoparticles and the fixed amount of the precursors.The results suggest the great potential of superionic conductor-mediated growth in composition regulation and bandgap engineering of chalcogenide nanowires/nanorods.
基金J.L.thanks financial supports from the National Key R&D Program of China(No.2021YFC2100100)the National Natural Science Foundation of China(No.21901157)+1 种基金the SJTU Global Strategic Partnership Fund(No.2020 SJTU-HUJI)the National Key Laboratory of Science and Technology on Micro/Nano Fabrication,China.
文摘Superionic conductors(SCs)exhibiting low ion migration activation energy(Ea)are critical to the performance of electrochemical energy storage devices such as solid-state batteries and fuel cells.However,it is challenging to obtain Ea experimentally and theoretically,and the artificial intelligence(AI)method is expected to bring a breakthrough in predicting Ea.Here,we proposed an AI platform(named AI-IMAE)to predict the Ea of cation and anion conductors,including Li^(+),Na^(+),Ag^(+),Al^(3+),Mg^(2+),Zn^(2+),Cu^((2)+),F^(−),and O^(2−),which is~105 times faster than traditional methods.The proposed AI-IMAE is based on crystal graph neural network models and achieves a holistic average absolute error of 0.19 eV,a median absolute error of 0.09 eV,and a Pearson coefficient of 0.92.Using AI-IMAE,we rapidly discovered 316 promising SCs as solid-state electrolytes and 129 SCs as cathode materials from 144,595 inorganic compounds.AI-IMAE is expected to completely solve the challenge of time-consuming Ea prediction and blaze a new trail for large-scale studies of SCs with excellent performance.As more experimental and high-precision theoretical data become available,AI-IMAE can train custom models and transfer the existing models to new models through transfer learning to constantly meet more demands.
基金support from the Zhejiang Provincial Natural Science Foundation of China(No.LQ23B030005)the National Natural Science Foundation of China(No.22208220).
文摘The practical application of Na metal batteries is severely hindered by uncontrolled Na dendrite growth and large volume fluctuations,which lead to safety hazards and poor cycling stability.Herein,we designed a composite 3D Ni foam skeleton modified with fast-ion conductor(FIC)networks to achieve dual ionic/electronic conductivity,enabling spatially guided Na^(+)deposition and confined growth.The FIC modification exhibits strong Na+affinity,which ensures uniform ion distribution and directs Na^(+)deposition preferentially within the porous Ni framework rather than on its surface.This unique structure facilitates region-induced deposition and spatial confinement of Na metal,effectively suppressing dendrite formation and mitigating volume expansion.Moreover,the FIC network significantly enhances Na+transport kinetics during plating/stripping processes,improving electrochemical reversibility.As a result,the FIC-modified 3D Ni host provides stable Na metal anodes with a prolonged cycling life and reduced polarization.The symmetric cells exhibit stable operation for 300 hours at 0.5 mA cm^(−2)and 2 mAh cm^(−2),while full cells demonstrate an outstanding capacity retention of 94.6%at 5C over 400 cycles.This work presents a rational electrode design strategy that combines guided ion redistribution and physical confinement to achieve dendrite-free Na metal anodes,providing new insights for developing high energy density Na-based batteries.
基金supported by the Basic Science Research Program through National Research Foundation of Korea(NRF)grant funded by the Ministry of Science and ICT(RS-2022-NR070534)supported by the National Research Council of Science&Technology(NST)grant by the Korea government(MSIT)(2710024139)。
文摘Li-argyrodites are promising solid electrolytes(SEs)for solid-state Li-ion batteries(SSLBs),but their large-scale industrial application remains a challenge.Conventional synthesis methods for SEs suffer from long reaction times and high energy consumption.In this study,we present a wet process for the synthesis of halogen-rich argyrodite Li_(6-a)PS_(5-a)Cl_(1+a)precursors(LPSCl_(1+a)-P,a=0–0.7)via an energysaving microwave-assisted process.Utilizing vibrational heating,we accelerate the formation of Liargyrodite precursor,even at excessive Cl-ion concentration,which significantly shortens the reaction time compared to traditional methods.After crystallization,we successfully synthesize the Liargyrodite,Li_(5.5)PS_(4.5)Cl_(1.5),which exhibits the superior ionic conductivity(7.8 mS cm^(-1))and low activation energy(0.23 eV)along with extremely low electric conductivity.The Li_(5.5)PS_(4.5)Cl_(1.5)exhibits superior Li compatibility owing to its high reversible striping/plating ability(over 5000 h)and high current density acceptability(1.3 mA cm^(-2)).It also exhibits excellent cycle reversibility and rate capability with NCM622 cathode(148.3 mA h g^(-1)at 1 C for 100 cycles with capacity retention of 85.6%).This finding suggests a potentially simpler and more scalable synthetic route to produce high-performance SEs.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12375285 and U2430205)the China Postdoctoral Science Foundation(Grant No.2022M722439)。
文摘Consideringα-RbCu_(4)Cl_(3)I_(2)is isostructural withα-RbAg4I5,in this work,we built a molecular dynamics simulation system of the former superionic conductor with an empirical pairwise potential model,which was verified on the latter crystal,including long-ranging Coulomb,short-ranging Born-Mayer,charge-dipole,and dipole-quadrupole interactions.The corresponding parameters were collected from the crystal structure and several reports of interionic potentials in alkali halides.The coordination number of fixed ions was examined,and the dynamic distribution of dissociative Cu+was described by the radial distribution function.The diffusion behavior of the ions was evaluated with mean square displacements and velocity auto-correlation functions.The diffusion coefficient of copper ions obtained is(47.9±6.1)×10-7cm^(2)/s,which is approximately 37 times that of the simulation result(1.3±0.1)×10^(-7)cm^(2)/s of silver inα-RbAg4I5at room temperature.In this work,the diffusion coefficient of Cu+was first discussed by molecule simulation,while there are few experimental reports.
基金This work was financially supported by the National Key Research and Development Program of China(No.2017YFB0102000)Major Program of the National Natural Science Foundation of China(No.51890865)the State Key Program of National Natural Science of China(No.61835014).
文摘Based on the excellent sodium ion mobility of sodium superionic conductor structures,Na_(3)V_(2)(PO_(4))_(3)materials have become promising cathode materials in sodium-ion batteries(SIBs).However,inadequate electronic transport of Na_(3)V_(2)(PO_(4))_(3)limits the cycling stability and rate performances in SIBs.In this work,high-performance conductive carbon-coated Na_(3)V_(2)(PO_(4))_(3)materials are obtained via a simple and facile ball-milling assisted solid-state method by utilizing citric acid as carbon sources.The carbon-coated composite electrodes display a high initial specific capacity of 111.6 mAh·g^(-1),and the specific capacity could retention reach 92.83%after 100 cycles at 1C with the high coulombic efficiency(99.95%).More importantly,the capacity of conductive carbon-coated nano-sized Na_(3)V_(2)(PO_(4))_(3)can remain 48.5 mAh·g^(-1) at 10℃after 3000 cycles(initial capacity of 101.2 mAh·g^(-1)).At the same time,high coulombic efficiency(near 100%)has little decay even at a high rate of 20℃during 1000 cycles,demonstrating the excellent cycling stability and remarkable rate performances,and showing potential in largescale productions and applications.
基金financially supported by the National Natural Science Foundation of China (Nos. 51472262 and 51625205)the Key Research Program of Chinese Academy of Sciences (No.KFZD-SW-421)the Shanghai Government (No. 15JC1400301)
文摘Copper sulfide Cu2S is a p-type semiconducting compound that has attracted great attentions in the thermoelectric （TE） community most recently. Considering the intrinsic ultralow lattice thermal conductivity, the enhancement of TE performance in CuzS should be achieved through improving its electrical transport properties. To achieve this goal, lithium element was doped into CuzS in this study. A series of Cu2_xLixS samples with different Li contents （x = 0, 0.005, 0.010, 0.050, and 0.100） was synthesized by the melting-annealing method. When x 〈 0.05, the Cuz_xLixS samples are stable and pure phases, having the same monoclinic structure with the pristine Cu2S at room temperature. The electrical conductivities in the Cu2_xLixS samples are greatly improved with the Li-doping content increasing due to the enhanced carrier concentrations. Meanwhile, doping Li into CuzS increases the ionic activation energy and lessens the influence of mobile Cu ions on the heat-carrying phonons. Thus, the thermal conductivities of the Li-doped Cu2S samples increase. A maximal figure of merit （zT） of 0.84 at 900 K is obtained in Cul.99Lio.018, about 133% improvement as compared with that in Cu2S matrix.
基金financially supported by the National Natural Science Foundation of China(Nos.51902238 and 52172234)the Fundamental Research Funds for the Central Universities(Nos.2020IVA069,2020IVB043 and 2021IVA020B)
文摘Rechargeable batteries based on solid-state electrolytes are of great interest and importance for the next-generation energy storage due to their high energy output and improved safety.For building the solid-state batteries,Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)represents a promising candidate as it features high chemical stability against air exposure and a high Na^(+)conductivity.NZSP pellets were usually calcined at a high temperature,and the high volatility of Na and P elements easily led to the formation of impurity phase.In this work,the effects of calcination temperature and stoichiometry on the phase purity and ionic conductivity of the NZSP electrolyte were studied.At an elevated sintering temperature,the NZSP electrolyte showed a high ionic conductivity owing to decreased porosity,and the highest ionic conductivity at 30℃was observed to be 2.75×10^(-5)S·cm^(-1)with an activation energy of 0.41 eV.For the stoichiometry,the introduction of 5 mol%excessive P results in formation of more Na_(3)PO_(4) and glass-like phase at the grain boundary,which caused the blurred grain boundary and reduced grain barrier,and effectively suppressed Na dendrite growth,then accounted for improved cycling performance of a Na‖Na symmetric cell.Our work provided insights on reasonable design and preparation of NZSP electrolyte towards practical realization of solid-state Na-metal batteries.
基金financially supported by the National Science Fund for Distinguished Young Scholars (No. 51725102)the Natural Science Foundation of China (Nos. 51871199, 51861145305)。
文摘Cu-and Ag-based superionic conductors are promising thermoelectric materials due to their good electrical properties and intrinsically low thermal conductivity. However, the poor electrical and thermal stability restrict their application. In this work, n-type pure phase Ag_(2) Te compound is synthesized by simply grinding elemental powders at room temperature and compacted by spark plasma sintering. It is found that, because of the migration of Ag+after the phase transition around 425 K, submicron pores are formed inside the samples during the electrical performance measurement, resulting in poor electrical stability and repeatability of Ag_(2) Te samples. However, Pb-doped Ag_(2-x)Pb_(x)Te(x = 0–0.05) specimens exhibit improved electrical stability by the precipitation of the secondary phase Pb Te in the Ag_(2) Te matrix, which is confirmed via cyclic electrical property measurement and microstructure characterization.A maximum z T = 0.72 is obtained at 570 K for x = 0.03 mainly due to the increased power factor.
基金Supported by the Major International Collaborative Project of the National Natural Science Foundation of China(No. 60574096)the Distinguished Young Scholars(No.60625301).
文摘Na superionic conductor（NASICON） nanoparticles were synthesized by a modified sol-gel method and sintered at a temperature range of 800--1000℃. The performance of the samples was characterized by the analysis methods of X-ray diffraction（XRD）, Fourier transform infrared spectroscopy（FTIR）, and transmission electron microscopy（TEM） as well as conductivity measurement. Compared with those sintered at other temperatures, the NASICON material sintered at 900 ℃ had the best crystalline structure and higher conductivity.
文摘The sharp decline in ionic conductivity at the liquid-solid phase transition is an intrinsic limitation of organic electrolytes.In conventional organic electrolytes(COEs),crystallization triggers pronounced conductivity loss and deviates from Arrhenius behavior,reflecting a fundamental shift in ion-transport mechanisms(Figure 1a)[1,2].In contrast,inorganic superionic conductors sustain fast ion transport in crystalline lattices when migration barriers are low and diffusion sites are energetically comparable[3,4].
基金supported by the National Key Research and Development Program of China (Grant No. 2019YFA0705700)National Natural Science Foundation of China (Grant No. 11704019)+1 种基金the Hundreds of Talents Program of Sun Yat-sen Universitythe Fundamental Research Funds for the Central Universities。
文摘As an ion conductor, the Al-doped Li1+xAlxGe2-x(PO4)3(LAGP) demonstrates the superionic Li diffusion behavior, however,without the convinced verifications. In this context, the density functional theory(DFT) calculations are employed to clarify the structural origin of the fast Li ion migration kinetics in LAGP solid electrolytes. The calculated results show that doping of Al leads to an emerging high-energy 36 f Li site, which plays an important role in promoting the Li diffusion and can largely lower the Li ion diffusion energy barrier. Moreover, the Li/Al antisite defect is investigated firstly, with which the Li ions are excited to occupy a relatively high energy site in LAGP. The obvious local structural distortion by Li/Al antisite results in the coordination change upon Li diffusion(lattice field distortion), which facilitates the Li diffusion significantly and is probably the main reason to account for the superionic diffusion phenomenon. Therefore, the occupation of Li at high-energy sites should be an effective method to establish the fast Li diffusion, which implies a rewarding avenue to build better Li-ion batteries.
基金supported by the National Key Research and Development Program of China(No.2016YFB0701100)the National Natural Science Foundation of China(Projects No.21673005 and 21621061)the High-performance Computing Platform of Peking University.
文摘Recent discoveries in the antiperovskite-class sodium superionic conductors call for a thorough mole cular dynamics(MD)study of sodium ion mobility,but the practical use of MD is often hindered by the accuracy-vs.-effciency dilemma.Here we applied the recently developed deep potential molecular dynamics(DeePMD)approach to investigate the ion mobility in Na_(3)OBr.With the deep potential model for Na_(3)OBr constructed based onfirst-principles density-functional theory(DFT)calculations,we directly calculate the Na+diffusion coeffcient at various temperatures,and obtain an activation energy of 0.42-0.43 eV.This in comparison with the 0 K migration barrier(0.41-0.43 eV)suggests that thefinite temperature effect is negligible for Na_(3)OBr.The model gives an extrapolated room temperature ionic conductivity of 1×10^(−4)-2×10^(−4)mS cm^(−1),roughly in the same order of magnitude as the experimental results.We also confirm the proportionality of the diffusion coeffcient with respect to the vacancy con centration,andfind that the migration barrier is relatively insensitive to the vacancy concentration.This work further demonstrates the promising role of the DeePMD method in the study of the transport pro perties of solid-state electrolytes.
