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
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
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
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
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
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
The recent report of near-ambient superconductivity in the nitrogen-doped lutetium hydride has attracted considerable attention.Subsequent follow-up studies confirmed the pressure-induced color changes in both N-free ...The recent report of near-ambient superconductivity in the nitrogen-doped lutetium hydride has attracted considerable attention.Subsequent follow-up studies confirmed the pressure-induced color changes in both N-free and N-doped LuH_(2) but failed to reproduce superconductivity. It remains a puzzle why the samples in the original report exhibited pronounced resistance anomaly reminiscent of the superconducting transition. Here, we show that percolation of metallic grains with high conductivity through the insulating surfaces in cold-pressed LuH_(2) samples can occasionally produce sharp resistance drops, which even display magnetic field and/or current dependences but stay far from zero resistance. The insulating surface of LuH2grain should be attributed to the modification of hydrogen stoichiometry or the contamination by oxygen/nitrogen, resulting in an increase of resistance by over six orders of magnitude. Such an effect is more significant than that discovered recently in LaH_(3±x), which may indicate that LuH_(2) can be a potential superionic conductor. Our results call for caution in asserting the resistivity drops as superconductivity and invalidate the background subtraction in analyzing the corresponding resistance data.展开更多
Developing cost-effective and reliable solid-state sodium batteries with superior performance is crucial for stationary energy storage.A key component in facilitating their application is a solid-state electrolyte wit...Developing cost-effective and reliable solid-state sodium batteries with superior performance is crucial for stationary energy storage.A key component in facilitating their application is a solid-state electrolyte with high conductivity and stability.Herein,we employed aliovalent cation substitution to enhance ionic conductivity while preserving the crystal structure.Optimized substitution of Y^(3+)with Zr^(4+)in Na_(5)YSi_(4)O_(12) introduced Naþion vacancies,resulting in high bulk and total conductivities of up to 6.5 and 3.3 mS cm^(-1),respectively,at room temperature with the composition Na_(4.92)Y_(0.92)Zr_(0.08)Si_(4)O_(12)(NYZS).NYZS shows exceptional electrochemical stability(up to 10 V vs.Naþ/Na),favorable interfacial compatibility with Na,and an excellent critical current density of 2.4 mA cm^(-2).The enhanced conductivity of Naþions in NYZS was elucidated using solid-state nuclear magnetic resonance techniques and theoretical simulations,revealing two migration routes facilitated by the synergistic effect of increased Naþion vacancies and improved chemical environment due to Zr^(4+)substitution.NYZS extends the list of suitable solid-state electrolytes and enables the facile synthesis of stable,low-cost Naþion silicate electrolytes.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
Sodium superionic conductor(NASICON)-type compounds have been regarded as promising cathodes for sodium-ion batteries(SIBs)due to their favorable ionic conductivity and robust structural stability.However,their high c...Sodium superionic conductor(NASICON)-type compounds have been regarded as promising cathodes for sodium-ion batteries(SIBs)due to their favorable ionic conductivity and robust structural stability.However,their high cost and relatively low energy density restrict their further practical application,which can be tailored by widening the operating voltages with earth-abundant elements such as Mn.Here,we propose a rational strategy of infusing Mn element in NASICON frameworks with sufficiently mobile sodium ions that enhances the redox voltage and ionic migration activity.The optimized structure of Na3.5Mn0.5V1.5(PO4)3/C is achieved and investigated systematically to be a durable cathode(76.6%capacity retention over 5,000 cycles at 20 C)for SIBs,which exhibits high reversible capacity(113.1 mAh·g^−1 at 0.5 C)with relatively low volume change(7.6%).Importantly,its high-areal-loading and temperature-resistant sodium ion storage properties are evaluated,and the full-cell configuration is demonstrated.This work indicates that this Na3.5Mn0.5V1.5(PO4)3/C composite could be a promising cathode candidate for SIBs.展开更多
Broadband optoelectronic devices intrigue enormous interests on account of their promising potential in optical communications,sensors and environmental monitoring.PbSe nanocrystals are promising candidates for the co...Broadband optoelectronic devices intrigue enormous interests on account of their promising potential in optical communications,sensors and environmental monitoring.PbSe nanocrystals are promising candidates for the construction of next-generation photodetectors due to their fascinating intrinsic properties and solution-processed compatibility with varied substrates.Here,we report the fabrication of a broadband photodetector on the basis of high-quality solution-processed PbSe nanorods in rock-salt phase grown along unconventionally anisotropic growth direction of<112>zone axis.The rock-salt PbSe nanorods are synthesized in solution phase over the catalysis of Ag2Se with relatively high-temperature body-centered cubic phase via a solution-solid-solid growth regime using oleylamine and oleic acid as solvents and stabilizer surfactants,from which the PbSe nanorods with the unconventionally anisotropic growth direction are controllably grown in size and shape in the synthetic procedure typically with about 17 nm in diameter and 58 nm in length on average.Meanwhile,the PbSe nanorods-based photodetector exhibits a broadband response from 405 to 1,064 nm with a high responsivity of 0.78 A·W^(-1)and a fast response time of 17.5μs.The response time is much faster in comparison with most of the PbSe-based photodetectors with response time in millisecond level.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
Sulfides have been widely acknowledged as one of the most promising solid electrolytes(SEs)for all-solid-state batteries(ASSBs)due to their superior ionic conductivity and favourable mechanical properties.However,the ...Sulfides have been widely acknowledged as one of the most promising solid electrolytes(SEs)for all-solid-state batteries(ASSBs)due to their superior ionic conductivity and favourable mechanical properties.However,the extremely poor air stability of sulfide SEs leads to destroyed structure/performance and release of toxic H_(2)S gas,which greatly limits mass-production/practical application of sulfide SEs and ASSBs.This review is designed to serve as an all-inclusive handbook for studying this critical issue.First,the research history and milestone breakthroughs of this field are reviewed,and this is followed by an in-depth elaboration of the theoretical paradigms that have been developed thus far,including the random network theory of glasses,hard and soft acids and bases(HSAB)theory,thermodynamic analysis and kinetics of interfacial reactions.Moreover,the characterization of air stability is reviewed from the perspectives of H2S generation,morphology evolution,mass change,component/structure variations and electrochemical performance.Furthermore,effective strategies for improving the air stabilities of sulfide SEs are highlighted,including H_(2)S absorbents,elemental substitution,design of new materials,surface engineering and sulfide-polymer composite electrolytes.Finally,future research directions are proposed for benign development of air stability for sulfide SEs and ASSBs.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
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
Digenite(Cu_(1.8)S)as a potential p-type thermoelectric(TE)material has attracted extensive attention due to its environmental benign,abundant resources and low cost of component elements.In this study,the TE properti...Digenite(Cu_(1.8)S)as a potential p-type thermoelectric(TE)material has attracted extensive attention due to its environmental benign,abundant resources and low cost of component elements.In this study,the TE properties of MnxCu_(1.8)S bulk samples prepared by mechanical alloying(MA)combined with spark plasma sintering(SPS)were investigated.Doping Mn would initially substitute Cu and tune the band structure of Cu1.8S with an enlarged band gap Eg.However,if Mn content is beyond the solubility limit of x=0.01 in Cu1.8S will cause the formation of MnS,which contributes to the formation of Cu-rich phases at 0.02 ≤x≤ 0.08.Benefiting from the synergetic scattering effect of point defects(Mn Cu,V_(S))and MnS,Cu1.96S,Cu1.97S,Cu2S phases,the lowest thermal conductivity k value of 0.75 W m^(-1) K^(-1) was obtained at 773 K for Mn0.08Cu1.8S.Along with the decreased k,the highest figure of merit ZT value of 0.92 at 773 K achieved in Mn0.08Cu1.8S bulk sample.A maximum engineering ZTeng of 0.3 and its efficiency hmax of about 6%were obtained at 323e773 K,which is almost 3 times than that of the pristine Cu1.8S(ηmax=2.2%).Introducing Mn in Cu1.8S is an effective and convenient strategy to improve TE performance.展开更多
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.
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.
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 Natural Science Foundation of China (Grant Nos. 12025408, 11921004, 11834016, and 11888101)the Beijing Natural Science Foundation (Grant No. Z190008)+1 种基金the National Key R&D Program of China (Grant Nos. 2021YFA1400200, and 2021YFA1400300)the Strategic Priority Research Program of CAS (Grant No. XDB33000000)。
文摘The recent report of near-ambient superconductivity in the nitrogen-doped lutetium hydride has attracted considerable attention.Subsequent follow-up studies confirmed the pressure-induced color changes in both N-free and N-doped LuH_(2) but failed to reproduce superconductivity. It remains a puzzle why the samples in the original report exhibited pronounced resistance anomaly reminiscent of the superconducting transition. Here, we show that percolation of metallic grains with high conductivity through the insulating surfaces in cold-pressed LuH_(2) samples can occasionally produce sharp resistance drops, which even display magnetic field and/or current dependences but stay far from zero resistance. The insulating surface of LuH2grain should be attributed to the modification of hydrogen stoichiometry or the contamination by oxygen/nitrogen, resulting in an increase of resistance by over six orders of magnitude. Such an effect is more significant than that discovered recently in LaH_(3±x), which may indicate that LuH_(2) can be a potential superionic conductor. Our results call for caution in asserting the resistivity drops as superconductivity and invalidate the background subtraction in analyzing the corresponding resistance data.
基金the China Scholarship Council (CSC,Grant Nos.201906200023,201906200016 and 201808080137,respectively)for financial supportfunding from the European Union's Horizon 2020 research,innovation program under the Marie Sklodowska-Curie grant agreement (No.101034329)the WINNING Normandy Program supported by the Normandy Region,France.
文摘Developing cost-effective and reliable solid-state sodium batteries with superior performance is crucial for stationary energy storage.A key component in facilitating their application is a solid-state electrolyte with high conductivity and stability.Herein,we employed aliovalent cation substitution to enhance ionic conductivity while preserving the crystal structure.Optimized substitution of Y^(3+)with Zr^(4+)in Na_(5)YSi_(4)O_(12) introduced Naþion vacancies,resulting in high bulk and total conductivities of up to 6.5 and 3.3 mS cm^(-1),respectively,at room temperature with the composition Na_(4.92)Y_(0.92)Zr_(0.08)Si_(4)O_(12)(NYZS).NYZS shows exceptional electrochemical stability(up to 10 V vs.Naþ/Na),favorable interfacial compatibility with Na,and an excellent critical current density of 2.4 mA cm^(-2).The enhanced conductivity of Naþions in NYZS was elucidated using solid-state nuclear magnetic resonance techniques and theoretical simulations,revealing two migration routes facilitated by the synergistic effect of increased Naþion vacancies and improved chemical environment due to Zr^(4+)substitution.NYZS extends the list of suitable solid-state electrolytes and enables the facile synthesis of stable,low-cost Naþion silicate electrolytes.
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This work was supported by the National Natural Science Foundation of China(Nos.51872334 and 51932011)the Innovation-Driven Project of Central South University(No.2020CX024).
文摘Sodium superionic conductor(NASICON)-type compounds have been regarded as promising cathodes for sodium-ion batteries(SIBs)due to their favorable ionic conductivity and robust structural stability.However,their high cost and relatively low energy density restrict their further practical application,which can be tailored by widening the operating voltages with earth-abundant elements such as Mn.Here,we propose a rational strategy of infusing Mn element in NASICON frameworks with sufficiently mobile sodium ions that enhances the redox voltage and ionic migration activity.The optimized structure of Na3.5Mn0.5V1.5(PO4)3/C is achieved and investigated systematically to be a durable cathode(76.6%capacity retention over 5,000 cycles at 20 C)for SIBs,which exhibits high reversible capacity(113.1 mAh·g^−1 at 0.5 C)with relatively low volume change(7.6%).Importantly,its high-areal-loading and temperature-resistant sodium ion storage properties are evaluated,and the full-cell configuration is demonstrated.This work indicates that this Na3.5Mn0.5V1.5(PO4)3/C composite could be a promising cathode candidate for SIBs.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.U1932150 and 21571166)Anhui Provincial Natural Science Foundation(No.1908085QB72).
文摘Broadband optoelectronic devices intrigue enormous interests on account of their promising potential in optical communications,sensors and environmental monitoring.PbSe nanocrystals are promising candidates for the construction of next-generation photodetectors due to their fascinating intrinsic properties and solution-processed compatibility with varied substrates.Here,we report the fabrication of a broadband photodetector on the basis of high-quality solution-processed PbSe nanorods in rock-salt phase grown along unconventionally anisotropic growth direction of<112>zone axis.The rock-salt PbSe nanorods are synthesized in solution phase over the catalysis of Ag2Se with relatively high-temperature body-centered cubic phase via a solution-solid-solid growth regime using oleylamine and oleic acid as solvents and stabilizer surfactants,from which the PbSe nanorods with the unconventionally anisotropic growth direction are controllably grown in size and shape in the synthetic procedure typically with about 17 nm in diameter and 58 nm in length on average.Meanwhile,the PbSe nanorods-based photodetector exhibits a broadband response from 405 to 1,064 nm with a high responsivity of 0.78 A·W^(-1)and a fast response time of 17.5μs.The response time is much faster in comparison with most of the PbSe-based photodetectors with response time in millisecond level.
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supported by the Key Program-Automobile Joint Fund of the National Natural Science Foundation of China(Grant No.U1964205)the Key R&D Project funded by the Department of Science and Technology of Jiangsu Province(Grant No.BE2020003)+4 种基金the General Program of the National Natural Science Foundation of China(Grant No.51972334)the General Program of the National Natural Science Foundation of Beijing(Grant No.2202058)the Cultivation Project of Leading Innovative Experts in Changzhou City(CQ20210003)the National Overseas High-Level Expert Recruitment Program(Grant No.E1JF021E11)the Talent Program of the Chinese Academy of Sciences,“Scientist Studio Program Funding”from the Yangtze River Delta Physics Research Center and the Tianmu Lake Institute of Advanced Energy Storage Technologies(Grant No.TIES-SS0001).
文摘Sulfides have been widely acknowledged as one of the most promising solid electrolytes(SEs)for all-solid-state batteries(ASSBs)due to their superior ionic conductivity and favourable mechanical properties.However,the extremely poor air stability of sulfide SEs leads to destroyed structure/performance and release of toxic H_(2)S gas,which greatly limits mass-production/practical application of sulfide SEs and ASSBs.This review is designed to serve as an all-inclusive handbook for studying this critical issue.First,the research history and milestone breakthroughs of this field are reviewed,and this is followed by an in-depth elaboration of the theoretical paradigms that have been developed thus far,including the random network theory of glasses,hard and soft acids and bases(HSAB)theory,thermodynamic analysis and kinetics of interfacial reactions.Moreover,the characterization of air stability is reviewed from the perspectives of H2S generation,morphology evolution,mass change,component/structure variations and electrochemical performance.Furthermore,effective strategies for improving the air stabilities of sulfide SEs are highlighted,including H_(2)S absorbents,elemental substitution,design of new materials,surface engineering and sulfide-polymer composite electrolytes.Finally,future research directions are proposed for benign development of air stability for sulfide SEs and ASSBs.
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supported by National Key R&D Program of China(Grant No.2018YFB0703600)the National Natural Science Foundation of China(Grant No.11474176)。
文摘Digenite(Cu_(1.8)S)as a potential p-type thermoelectric(TE)material has attracted extensive attention due to its environmental benign,abundant resources and low cost of component elements.In this study,the TE properties of MnxCu_(1.8)S bulk samples prepared by mechanical alloying(MA)combined with spark plasma sintering(SPS)were investigated.Doping Mn would initially substitute Cu and tune the band structure of Cu1.8S with an enlarged band gap Eg.However,if Mn content is beyond the solubility limit of x=0.01 in Cu1.8S will cause the formation of MnS,which contributes to the formation of Cu-rich phases at 0.02 ≤x≤ 0.08.Benefiting from the synergetic scattering effect of point defects(Mn Cu,V_(S))and MnS,Cu1.96S,Cu1.97S,Cu2S phases,the lowest thermal conductivity k value of 0.75 W m^(-1) K^(-1) was obtained at 773 K for Mn0.08Cu1.8S.Along with the decreased k,the highest figure of merit ZT value of 0.92 at 773 K achieved in Mn0.08Cu1.8S bulk sample.A maximum engineering ZTeng of 0.3 and its efficiency hmax of about 6%were obtained at 323e773 K,which is almost 3 times than that of the pristine Cu1.8S(ηmax=2.2%).Introducing Mn in Cu1.8S is an effective and convenient strategy to improve TE performance.