The ion conductivity of a solid-state ion conductor generally increases exponentially upon reduction in ionmigration barrier.For prevalent cathode material LiCoO_(2),the room-temperature ion conductivity and migration...The ion conductivity of a solid-state ion conductor generally increases exponentially upon reduction in ionmigration barrier.For prevalent cathode material LiCoO_(2),the room-temperature ion conductivity and migrationbarrier are respectively around 10^(−4)S/cm and 0.3 eV.In this Letter,through first-principles calculations we predictthe existence of 1D superionicity as the Li ions in O_(2)LiCoO_(2)are transformed into Zn_(0.5)CoO_(2)or Li_(0.5)CoO_(2)via cation-exchange reaction or deintercalation.The ion migration barriers(0.01-0.02 eV)even lower than roomtemperature∼𝑘B𝑇are reduced by more than an order of magnitude compared with LiCoO_(2),which are facilitatedby facile transition of mobile ions between two coordination configurations.The room-temperature ion conductivityis estimated to be over 50 S/cm,enhanced by 2-3 orders of magnitude compared with the current highestreported value.Such unprecedented superionicity may also exist in other similar layered ion conductors,whichmay lead to technical advances and exotic effects such as ultrafast ion batteries and quantized ferroelectricity.展开更多
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
Traditional metal sulfides used as anodes for sodium-ion batteries are hindered by sluggish kinetics,which limits their rate performance.Previous attempts to address this issue focused on nanostructured configurations...Traditional metal sulfides used as anodes for sodium-ion batteries are hindered by sluggish kinetics,which limits their rate performance.Previous attempts to address this issue focused on nanostructured configurations with conductive frameworks.However,these nanomaterials often suffer from low packing density and the tendency for nanoparticles to agglomerate,posing significant challenges for practical applications.To overcome these limitations,this study presents a novel bimetal superionic anode material Cu_(3.21)Bi_(4.79)S_(9),which effectively resolves the conflict between sluggish kinetics and micrometer-scale particle size.By leveraging the vacancies created by free Cu and Bi atoms,this material forms rapid migration channels during sodium insertion and extraction,significantly reducing the migration barriers for sodium ions.The development of micrometer-scale Cu_(3.21)Bi_(4.79)S_(9)enables ultrafast chargingdischarging capabilities,achieving a reversible capacity of 325.5 mAh g^(-1)after 4000 cycles at a high rate of 45 C(15 A g^(-1)).This work marks a significant advancement in the field by offering a solution to the inherent trade-off between high capacity and rate performance in coarse-grained materials,reducing the need for reliance on nanostructured configurations for next-generation high-capacity anode materials.展开更多
All-solid-state lithium ion batteries(ASSLIBs)have attracted much attention due to their high safety and increased energy density,which have become a substitute to conventional liquid electrolyte batteries[1].The deve...All-solid-state lithium ion batteries(ASSLIBs)have attracted much attention due to their high safety and increased energy density,which have become a substitute to conventional liquid electrolyte batteries[1].The development of high-performance solid electrolyte is the key to the development of solid-state battery technology.Solid-state electrolyte(SSE)materials should have high ionic conductivity,poor electronic conductivity,wide electrochemical window,and low electrode and electrolyte interface resistance.展开更多
Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceram...Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceramic fillers.Here,a host–vip inversion engineering strategy is proposed to develop superionic CSEs using cost-effective SiO_(2) nanoparticles as passive ceramic hosts and poly(vinylidene fluoride-hexafluoropropylene)(PVH)microspheres as polymer vips,forming an unprecedented“polymer vip-in-ceramic host”(i.e.,PVH-in-SiO_(2))architecture differing from the traditional“ceramic vip-in-polymer host”.The PVH-in-SiO_(2) exhibits excellent Li-salt dissociation,achieving high-concentration free Li+.Owing to the low diffusion energy barriers and high diffusion coefficient,the free Li+is thermodynamically and kinetically favorable to migrate to and transport at the SiO_(2)/PVH interfaces.Consequently,the PVH-in-SiO_(2) delivers an exceptional ionic conductivity of 1.32.10−3 S cm−1 at 25℃(vs.typically 10−5–10−4 S cm−1 using high-cost active ceramics),achieved under an ultralow residual solvent content of 2.9 wt%(vs.8–15 wt%in other CSEs).Additionally,PVH-in-SiO_(2) is electrochemically stable with Li anode and various cathodes.Therefore,the PVH-in-SiO_(2) demonstrates excellent high-rate cyclability in LiFePO4|Li full cells(92.9%capacity-retention at 3C after 300 cycles under 25℃)and outstanding stability with high-mass-loading LiFePO4(9.2 mg cm−1)and high-voltage NCM622(147.1 mAh g−1).Furthermore,we verify the versatility of the host–vip inversion engineering strategy by fabricating Na-ion and K-ion-based PVH-in-SiO_(2) CSEs with similarly excellent promotions in ionic conductivity.Our strategy offers a simple,low-cost approach to fabricating superionic CSEs for large-scale application of solid-state Li metal batteries and beyond.展开更多
The various theoretical and experimental models for ion conduction mechanism of fast ion conducting （FIC） glass electrolytes have been reported in the present review paper. Some characterization techniques of FIC gl...The various theoretical and experimental models for ion conduction mechanism of fast ion conducting （FIC） glass electrolytes have been reported in the present review paper. Some characterization techniques of FIC glasses are presented. The experimental methods for determination of some ion transport parameters viz ionic conductivity （σ）, ionic mobility （μ）, mobile ion concentration （n）, ionic drift velocity （Vd）, ionic transference number （tion） and activation energies of FIC glasses are explained. The solid state battery fabrication by using some FIC glasses is also reported.展开更多
Hydrogen and lithium,along with their compounds,are crucial materials for nuclear fusion research.High-pressure studies have revealed intricate structural transitions in all these materials.However,research on lithium...Hydrogen and lithium,along with their compounds,are crucial materials for nuclear fusion research.High-pressure studies have revealed intricate structural transitions in all these materials.However,research on lithium hydrides beyond LiH has mostly focused on the low-temperature regime.Here,we use density functional theory and ab initio molecular dynamics simulations to investigate the behavior of LiH_(2),a hydrogen-rich compound,near its melting point.Our study is particularly relevant to the low-pressure region of the compression pathway of lithium hydrides toward fusion.We discovered a premelting superionic phase transition in LiH_(2)that has significant implications for its mass transportation,elastic properties,and sound velocity.The theoretical boundary for the superionic transition and melting temperature was then determined.In contrast,we also found that the primary compound of lithium hydrides,LiH,does not exhibit a superionic transition.These findings have important implications for optimizing the compression path to achieve the ignition condition in inertial confinement fusion research,especially when lithium tritium-deuteride(LiTD)is used as the fuel.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
Since the work of Penrose and Hameroff the possibility is discussed that the location of human memory and consciousness could be connected with tubulin microtubules. If one would use superionic nano-materials rolled u...Since the work of Penrose and Hameroff the possibility is discussed that the location of human memory and consciousness could be connected with tubulin microtubules. If one would use superionic nano-materials rolled up to microtubules with an electrolyte inside the formed channels mediating fast ionic exchange of protons respectively lithium ions, it seems to be possible to write into such materials whole image arrays (pictures) under the action of the complex electromagnetic spectrum that composes these images. The same material and architecture may be recommended for super-computers. Especially microtubules with a protofilament number of 13 are the most important to note. We connected such microtubules before with Fibonacci nets composed of 13 sub-cells that were helically rolled up to deliver suitable channels. Our recent Fibonacci analysis of Wadsley-Roth shear phases such as niobium tungsten oxide , exhibiting channels for ultra-fast lithium-ion diffusion, suggests to use these materials, besides super-battery main application, in form of nanorods or microtubules as effectively working superionic memory devices for computers that work ultra-fast with the complex effectiveness of human brains. Finally, we pose the question, whether dark matter, ever connected with ultrafast movement of ordinary matter, may be responsible for synchronization between interactions of human brains and consciousness.展开更多
Superionic transition(SIT)is an extraordinary phenomenon where a compound attains high ionic conductivity through anomalous disordering of mobile-ion sublattice.Comprehending SIT offers notable prospects for the advan...Superionic transition(SIT)is an extraordinary phenomenon where a compound attains high ionic conductivity through anomalous disordering of mobile-ion sublattice.Comprehending SIT offers notable prospects for the advancement of superionic conductors(SICs)for diverse applications.However,the investigation of SIT is impeded by its intricate and stochastic characteristics,coupled with the absence of adequate methods for characterizing,quantifying,and analyzing its microscopic properties.Here we show that the SIT can be discerned through the dynamic signatures of disordering events underlying the increase in ionic conductivity.The adoption of a dynamic perspective as opposed to the conventional treatment of equilibrium properties brings significant advantage to scrutinize the microscopic characteristics of SIT.Our results show the SIT in the prototypical family of fluorite compounds is characterized by the scaleinvariant disordering dynamics independent of temperature or extent of disorder.The observation of scale-invariance in the absence of external tuning implies that the superionic conduction is self-tuned to criticality by intrinsic dynamics.The connection between ionic diffusion and self-organized criticality provides a novel platform for understanding,analyzing,and manipulating SIT towards better SICs.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
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）-...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
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
I. INTRODUCTIONIn recent years, people have conducted a lot of experiments and valuable theoretical studies on amorphous superionic conductors. From their results, the σ～ω property of amorphous superionic conductor...I. INTRODUCTIONIn recent years, people have conducted a lot of experiments and valuable theoretical studies on amorphous superionic conductors. From their results, the σ～ω property of amorphous superionic conductors can generally be concluded as follows:展开更多
The results from the molecular dynamics simulations on crystalline, superionic, molten and quenched-amorphous states of calcium fluoride system are reported. The Ca++ and F- sublattices are studied by using the method...The results from the molecular dynamics simulations on crystalline, superionic, molten and quenched-amorphous states of calcium fluoride system are reported. The Ca++ and F- sublattices are studied by using the method of bond order parameters. The result shows that both Ca++ and F- sublattices can be described with the bond-orientation normal distribution model. In the superionic phase the Ca++ cations keep their original stable fcc frame, but in the F- case random distortion generates from their original simple cubic (sc) structure. The simulation on the molten phase gives three radial distribution functions that are difficult to separate from the experimental X-ray diffraction data. The simulation of quenched-amorphous state shows that a dense random packing of equivalent spheres centered by Ca++ cations occurs in the system simulated. However, the system quenched is not stable enough because the Ca++ cation and F- anions around it do not form themselves into a certain configuration.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
基金supported by the National Natural Science Foundation of China(Grant No.22073034)。
文摘The ion conductivity of a solid-state ion conductor generally increases exponentially upon reduction in ionmigration barrier.For prevalent cathode material LiCoO_(2),the room-temperature ion conductivity and migrationbarrier are respectively around 10^(−4)S/cm and 0.3 eV.In this Letter,through first-principles calculations we predictthe existence of 1D superionicity as the Li ions in O_(2)LiCoO_(2)are transformed into Zn_(0.5)CoO_(2)or Li_(0.5)CoO_(2)via cation-exchange reaction or deintercalation.The ion migration barriers(0.01-0.02 eV)even lower than roomtemperature∼𝑘B𝑇are reduced by more than an order of magnitude compared with LiCoO_(2),which are facilitatedby facile transition of mobile ions between two coordination configurations.The room-temperature ion conductivityis estimated to be over 50 S/cm,enhanced by 2-3 orders of magnitude compared with the current highestreported value.Such unprecedented superionicity may also exist in other similar layered ion conductors,whichmay lead to technical advances and exotic effects such as ultrafast ion batteries and quantized ferroelectricity.
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.
基金the financial support of the National Natural Science Foundation of China(Grant No.21975036)the Fundamental Research Funds for the Central Universities(Grant No.3132023503).
文摘Traditional metal sulfides used as anodes for sodium-ion batteries are hindered by sluggish kinetics,which limits their rate performance.Previous attempts to address this issue focused on nanostructured configurations with conductive frameworks.However,these nanomaterials often suffer from low packing density and the tendency for nanoparticles to agglomerate,posing significant challenges for practical applications.To overcome these limitations,this study presents a novel bimetal superionic anode material Cu_(3.21)Bi_(4.79)S_(9),which effectively resolves the conflict between sluggish kinetics and micrometer-scale particle size.By leveraging the vacancies created by free Cu and Bi atoms,this material forms rapid migration channels during sodium insertion and extraction,significantly reducing the migration barriers for sodium ions.The development of micrometer-scale Cu_(3.21)Bi_(4.79)S_(9)enables ultrafast chargingdischarging capabilities,achieving a reversible capacity of 325.5 mAh g^(-1)after 4000 cycles at a high rate of 45 C(15 A g^(-1)).This work marks a significant advancement in the field by offering a solution to the inherent trade-off between high capacity and rate performance in coarse-grained materials,reducing the need for reliance on nanostructured configurations for next-generation high-capacity anode materials.
文摘All-solid-state lithium ion batteries(ASSLIBs)have attracted much attention due to their high safety and increased energy density,which have become a substitute to conventional liquid electrolyte batteries[1].The development of high-performance solid electrolyte is the key to the development of solid-state battery technology.Solid-state electrolyte(SSE)materials should have high ionic conductivity,poor electronic conductivity,wide electrochemical window,and low electrode and electrolyte interface resistance.
基金financial support from the National Natural Science Foundation of China(Nos.52250010 and 52201242)the 261 Project of MIIT,Natural Science Foundation of Jiangsu Province(No.BK20240179)the Young Elite Scientists Sponsorship Program by CAST(No.2021QNRC001).
文摘Composite solid electrolytes(CSEs)are promising for solid-state Li metal batteries but suffer from inferior room-temperature ionic conductivity due to sluggish ion transport and high cost due to expensive active ceramic fillers.Here,a host–vip inversion engineering strategy is proposed to develop superionic CSEs using cost-effective SiO_(2) nanoparticles as passive ceramic hosts and poly(vinylidene fluoride-hexafluoropropylene)(PVH)microspheres as polymer vips,forming an unprecedented“polymer vip-in-ceramic host”(i.e.,PVH-in-SiO_(2))architecture differing from the traditional“ceramic vip-in-polymer host”.The PVH-in-SiO_(2) exhibits excellent Li-salt dissociation,achieving high-concentration free Li+.Owing to the low diffusion energy barriers and high diffusion coefficient,the free Li+is thermodynamically and kinetically favorable to migrate to and transport at the SiO_(2)/PVH interfaces.Consequently,the PVH-in-SiO_(2) delivers an exceptional ionic conductivity of 1.32.10−3 S cm−1 at 25℃(vs.typically 10−5–10−4 S cm−1 using high-cost active ceramics),achieved under an ultralow residual solvent content of 2.9 wt%(vs.8–15 wt%in other CSEs).Additionally,PVH-in-SiO_(2) is electrochemically stable with Li anode and various cathodes.Therefore,the PVH-in-SiO_(2) demonstrates excellent high-rate cyclability in LiFePO4|Li full cells(92.9%capacity-retention at 3C after 300 cycles under 25℃)and outstanding stability with high-mass-loading LiFePO4(9.2 mg cm−1)and high-voltage NCM622(147.1 mAh g−1).Furthermore,we verify the versatility of the host–vip inversion engineering strategy by fabricating Na-ion and K-ion-based PVH-in-SiO_(2) CSEs with similarly excellent promotions in ionic conductivity.Our strategy offers a simple,low-cost approach to fabricating superionic CSEs for large-scale application of solid-state Li metal batteries and beyond.
基金DST,New Delhi for providing financial assistance through the Fast Track Young Scientist Research Project(No.SR/FTP/PS-23/2009)
文摘The various theoretical and experimental models for ion conduction mechanism of fast ion conducting （FIC） glass electrolytes have been reported in the present review paper. Some characterization techniques of FIC glasses are presented. The experimental methods for determination of some ion transport parameters viz ionic conductivity （σ）, ionic mobility （μ）, mobile ion concentration （n）, ionic drift velocity （Vd）, ionic transference number （tion） and activation energies of FIC glasses are explained. The solid state battery fabrication by using some FIC glasses is also reported.
基金Project supported by the National Key Research and Development Program of China(Grant No.2021YFB3802300)the National Natural Science Foundation of China(Grant No.11672274)the NSAF(Grant No.U1730248)。
文摘Hydrogen and lithium,along with their compounds,are crucial materials for nuclear fusion research.High-pressure studies have revealed intricate structural transitions in all these materials.However,research on lithium hydrides beyond LiH has mostly focused on the low-temperature regime.Here,we use density functional theory and ab initio molecular dynamics simulations to investigate the behavior of LiH_(2),a hydrogen-rich compound,near its melting point.Our study is particularly relevant to the low-pressure region of the compression pathway of lithium hydrides toward fusion.We discovered a premelting superionic phase transition in LiH_(2)that has significant implications for its mass transportation,elastic properties,and sound velocity.The theoretical boundary for the superionic transition and melting temperature was then determined.In contrast,we also found that the primary compound of lithium hydrides,LiH,does not exhibit a superionic transition.These findings have important implications for optimizing the compression path to achieve the ignition condition in inertial confinement fusion research,especially when lithium tritium-deuteride(LiTD)is used as the fuel.
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.
文摘Since the work of Penrose and Hameroff the possibility is discussed that the location of human memory and consciousness could be connected with tubulin microtubules. If one would use superionic nano-materials rolled up to microtubules with an electrolyte inside the formed channels mediating fast ionic exchange of protons respectively lithium ions, it seems to be possible to write into such materials whole image arrays (pictures) under the action of the complex electromagnetic spectrum that composes these images. The same material and architecture may be recommended for super-computers. Especially microtubules with a protofilament number of 13 are the most important to note. We connected such microtubules before with Fibonacci nets composed of 13 sub-cells that were helically rolled up to deliver suitable channels. Our recent Fibonacci analysis of Wadsley-Roth shear phases such as niobium tungsten oxide , exhibiting channels for ultra-fast lithium-ion diffusion, suggests to use these materials, besides super-battery main application, in form of nanorods or microtubules as effectively working superionic memory devices for computers that work ultra-fast with the complex effectiveness of human brains. Finally, we pose the question, whether dark matter, ever connected with ultrafast movement of ordinary matter, may be responsible for synchronization between interactions of human brains and consciousness.
文摘Superionic transition(SIT)is an extraordinary phenomenon where a compound attains high ionic conductivity through anomalous disordering of mobile-ion sublattice.Comprehending SIT offers notable prospects for the advancement of superionic conductors(SICs)for diverse applications.However,the investigation of SIT is impeded by its intricate and stochastic characteristics,coupled with the absence of adequate methods for characterizing,quantifying,and analyzing its microscopic properties.Here we show that the SIT can be discerned through the dynamic signatures of disordering events underlying the increase in ionic conductivity.The adoption of a dynamic perspective as opposed to the conventional treatment of equilibrium properties brings significant advantage to scrutinize the microscopic characteristics of SIT.Our results show the SIT in the prototypical family of fluorite compounds is characterized by the scaleinvariant disordering dynamics independent of temperature or extent of disorder.The observation of scale-invariance in the absence of external tuning implies that the superionic conduction is self-tuned to criticality by intrinsic dynamics.The connection between ionic diffusion and self-organized criticality provides a novel platform for understanding,analyzing,and manipulating SIT towards better SICs.
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.
文摘I. INTRODUCTIONIn recent years, people have conducted a lot of experiments and valuable theoretical studies on amorphous superionic conductors. From their results, the σ～ω property of amorphous superionic conductors can generally be concluded as follows:
基金Project supported by the National Natural Science Foundation of China.
文摘The results from the molecular dynamics simulations on crystalline, superionic, molten and quenched-amorphous states of calcium fluoride system are reported. The Ca++ and F- sublattices are studied by using the method of bond order parameters. The result shows that both Ca++ and F- sublattices can be described with the bond-orientation normal distribution model. In the superionic phase the Ca++ cations keep their original stable fcc frame, but in the F- case random distortion generates from their original simple cubic (sc) structure. The simulation on the molten phase gives three radial distribution functions that are difficult to separate from the experimental X-ray diffraction data. The simulation of quenched-amorphous state shows that a dense random packing of equivalent spheres centered by Ca++ cations occurs in the system simulated. However, the system quenched is not stable enough because the Ca++ cation and F- anions around it do not form themselves into a certain configuration.
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.
