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1.
《Ceramics International》2021,47(20):28377-28383
In order to use sulfide all-solid-state batteries as power sources of electric devices, sulfide solid electrolytes with high ionic conductivity and high air-stability must be developed. Li3PS4 electrolytes have been used in all-solid-state batteries because of their relatively high ionic conductivity (4 × 10 −4 S cm−1 at 25 °C) and higher air-stability than those of other Li2S–P2S5 type solid electrolytes. Herein, the Li4SnS4–Li3PS4 system was investigated to (1) increase the ionic conductivity of Li3PS4 using excess Li carriers and (2) improve the air-stability of Li3PS4 by introducing air-stable Sn–S bonds. The structure, ionic conductivity, and air-stability of xLi4SnS4·(1−x)Li3PS4 were systematically investigated; the results showed that adding small amounts of Li4SnS4 to Li3PS4 glass and glass-ceramic enhanced their ionic conductivity and air-stability without degrading their electrochemical stability. In particular, the 0.3Li4SnS4·0.7Li3PS4 glass-ceramic showed an ionic conductivity of 8.1 × 10 −4 S cm−1 at 25 °C and generated only a small amount of H2S gas (3 ppm [0.3 cm3 g−1]) when it was dissolved in water. Hence, xLi4SnS4·(1−x)Li3PS4 solid electrolytes can be used as alternatives to the conventional Li3PS4 electrolyte because of their various advantages and a simple preparation method that involves adding only SnS2 to conventional starting materials.  相似文献   

2.
Lithium ion conductors with garnet‐type structure are promising candidates for applications in all solid‐state lithium ion batteries, because these materials present a high chemical stability against Li metal and a rather high Li+ conductivity (10?3–10?4 S/cm). Producing densified Li‐ion conductors by lowering sintering temperature is an important issue, which can achieve high Li conductivity in garnet oxide by preventing the evaporation of lithium and a good Li‐ion conduction in grain boundary between garnet oxides. In this study, we concentrate on the use of sintering additives to enhance densification and microstructure of Li7La3ZrNbO12 at sintering temperature of 900°C. Glasses in the LiO2‐B2O3‐SiO2‐CaO‐Al2O3 (LBSCA) and BaO‐B2O3‐SiO2‐CaO‐Al2O3 (BBSCA) system with low softening temperature (<700°C) were used to modify the grain‐boundary resistance during sintering process. Lithium compounds with low melting point (<850°C) such as LiF, Li2CO3, and LiOH were also studied to improve the rearrangement of grains during the initial and middle stages of sintering. Among these sintering additives, LBSCA and BBSCA were proved to be better sintering additives at reducing the porosity of the pellets and improving connectivity between the grains. Glass additives produced relative densities of 85–92%, whereas those of lithium compounds were 62–77%. Li7La3ZrNbO12 sintered with 4 wt% of LBSCA at 900°C for 10 h achieved a rather high relative density of 85% and total Li‐ion conductivity of 0.8 × 10?4 S/cm at room temperature (30°C).  相似文献   

3.
A phase diagram is constructed for the quasi‐binary Li4GeS4–Li3PS4 system containing the lithium superionic conductor Li10GeP2S12 (LGPS), having an LGPS‐type structure, and the β‐Li3PS4‐type phase, having a thio‐LISICON structure. The LGPS and thio‐LISICON intermediate compounds are found to exhibit solid solution ranges and show incongruent melting at 650°C and 560°C, respectively. The end‐member Li4GeS4 has a compositional range of 0 < < 0.3 in [(1?k) Li4GeS4 + k Li3PS4], while the other end‐member γ‐Li3PS4 has no solid solution range. The crystal structures appearing in the binary systems are the α‐, β‐, and γ‐type Li3PS4 structures and the LGPS‐type structure, and these are formed by PS4 tetrahedra with different arrangements in each structure. The phase and structural relationships between the compounds appearing in the Li4GeS4–Li3PS4 system are thus clarified.  相似文献   

4.
High ionic conductivity, low grain boundary impedance, and stable electrochemical property have become the focus for all-solid-state lithium–sulfur batteries (ASSLSB). One of the approaches is to promote the rapid diffusion of lithium ions by regulating the chemical bond interactions within the framework. The structure control of P5+ substitution for Sn4+ on lithium-ion transport was explored for a series of Li3PS4–Li4SnS4 glass–ceramic electrolytes. Results showed that the grain boundary impedance of the glass electrolyte was reduced after heat treatments. The formation of LiSnPS microcrystals, a good superionic conductor, was detected by X-ray diffraction tests. Electrochemical experiments obtained the highest conductivity of 29.5 S cm−1 at 100°C and stable electrochemical window from –0.1 to 5 V at 25°C. In addition, the cell battery was assembled with prepared electrolyte, which is promoted as a candidate solid electrolyte material with improved performance for ASSLSB.  相似文献   

5.
Ta‐doped cubic phase Li7La3Zr2O12 (LLZ) lithium garnet received considerable attention in recent times as prospective electrolyte for all‐solid‐state lithium battery. Although the conductivity has been improved by stabilizing the cubic phase with the Ta5+ doping for Zr4+ in LLZ, the density of the pellet was found to be relatively poor with large amount of pores. In addition to the high Li+ conductivity, density is also an essential parameter for the successful application of LLZ as solid electrolyte membrane in all‐solid‐state lithium battery. Systematic investigations carried out through this work indicated that the optimal Li concentration of 6.4 (i.e., Li6.4La3Zr1.4Ta0.6O12) is required to obtain phase pure, relatively dense and high Li+ conductive cubic phase in Li7?xLa3Zr2?xTaxO12 solid solutions. Effort has been also made in this work to enhance the density and Li+ conductivity of Li6.4La3Zr1.4Ta0.6O12 further through the Li4SiO4 addition. A maximized room‐temperature (33°C) total (bulk + grain boundary) Li+ conductivity of 3.7 × 10?4 S/cm and maximized relative density of 94% was observed for Li6.4La3Zr1.4Ta0.6O12 added with 1 wt% of Li4SiO4.  相似文献   

6.
Sulfide glass-ceramic electrolytes with Li+ or Na+ ion conduction have been developed in last decade. High-temperature phases of Li7P3S11 and cubic Na3PS4 are precipitated from mother glasses, and the obtained glass-ceramics show higher conductivity than the mother glasses. It is difficult to synthesize those high-temperature phases by conventional solid-state reaction, and glass electrolytes are thus important as a precursor for forming high-temperature phases. The highest conductivities at 25°C of 1.1 × 10−2 S/cm for Li+ ion conductor (Li7P3S11) and 7.4 × 10−4 S/cm for Na+ ion conductor (Na3.06P0.94Si0.06S4) are achieved in sulfide glass-ceramic electrolytes. All-solid-state batteries with sulfide glass-ceramic electrolytes were fabricated by cold press at room temperature. Sulfide electrolytes have favorable mechanical properties to form favorable solid–solid contacts in solid-state batteries by pressing without heat treatment. All-solid-state Li-In/S and Na-Sn/TiS2 cells using sulfide glass-ceramic electrolytes operate as secondary batteries and exhibit good cycle performance at room temperature.  相似文献   

7.
We report the effect of oxygen mixing percentage (OMP) on structural, microstructural, dielectric, linear, and nonlinear optical properties of Dy2O3‐doped (K0.5Na0.5)NbO3 thin films. The (K0.5Na0.5)NbO3 + 0.5 wt%Dy2O3 (KNN05D) ferroelectric thin films were deposited on to quartz and Pt/Ti/SiO2/Si substrates by RF magnetron sputtering. An increase in the refractive index from 2.08 to 2.21 and a decrease in the optical bandgap from 4.30 to 4.28 eV indicate the improvement in crystallinity, which is also confirmed from Raman studies. A high relative permittivity (εr=281‐332) and low loss tangent (tanδ=1.2%‐1.9%) were obtained for the films deposited in 100% OMP, measured at microwave frequencies (5‐15 GHz). The leakage current of the films found to be as low as 9.90×10?9 A/cm2 at 150 kV/cm and Poole‐Frenkel emission is the dominant conduction mechanism in the films. The third order nonlinear optical properties of the KNN05D films were investigated using modified single beam z‐scan method. The third order nonlinear susceptibility (?χ(3)?) values of KNN05D films increased from 0.69×10?3 esu to 1.40×10?3 esu with an increase in OMP. The larger and positive nonlinear refractive index n2=7.04×10?6 cm2/W, and nonlinear absorption coefficient β=1.70 cm/W were obtained for the 100% OMP film, indicating that KNN05D films are good candidates for the applications in nonlinear photonics and high‐frequency devices.  相似文献   

8.
A group of polyethylene oxide (PEO)LiClO4‐Li1.3Al0.3Ti1.7(PO4)3 composite polymer electrolyte (CPE) films was prepared by the solution‐cast method. In each film, EO/Li = 8 and the Li1.3Al0.3Ti1.7(PO4)3 content of 15 wt % were fixed, but the number averaged molecular weight of PEO (Mn) was altered from 5 to 7 × 104 to 106, 2.2–2.7 × 106, 3–4 × 106, 4–5 × 106, and 5.5–6 × 106, respectively. Several techniques including X‐ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), and electrical impedance spectroscopy (EIS) were used to characterize the CPE films. LiClO4 was found to have a strong tendency to complex with PEO, but Li1.3Al0.3Ti1.7(PO4)3 was rather dispersed in PEO matrix. DSC analysis revealed that the amorphous phase was dominant in the CPE films although the PEOs before‐use was considerably crystalline. SEM study showed smooth and homogeneous morphologies of the films with low molecular weight PEO and a dual phase characteristic for those with high molecular weight PEO. EIS results indicated that the CPE films are all ionic conductor and the conducting behavior obeys Vogel‐Tamman‐Fulcher (VTF) equation. The parameters in VTF equation were obtained and discussed by taking into considerations PEO molecular weights and crystallinities of the CPE films. Of all the films, the one with PEO with the smallest Mn = 5–7 × 104 had the maximum conductivity, i.e., 1.590 × 10?5 S cm?1 at room temperature and 1.886 × 10?3 S cm?1 at 373 K. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4269–4275, 2006  相似文献   

9.
Li ion conducting polymer electrolyte films were prepared based on poly(vinyl alcohol) (PVA) with 5, 10, 15, 20, 25 and 30 wt% lithium iron phosphate (LiFePO4) salt using a solution-casting technique. X-ray diffraction (XRD) was used to determine the complexation of the polymer with LiFePO4 salt. Differential scanning (DSC) calorimetry was used to determine the melting temperatures of the pure PVA and complexed films. The maximum ionic conductivity was found to be 1.18 × 10−5 S cm−1 for (PVA:LiFePO4) (75:25) film, which increased to 3.12 × 10−5 S cm−1 upon the addition of propylene carbonate (PC) plasticizer at ambient temperature. The Li+ ion transport number was found to be 0.40 for (PVA: LiFePO4) (75:25) film using AC impedance and DC polarization methods. Dielectric studies were performed for these polymer electrolyte films in the frequency range of 10 Hz to 10 MHz at different temperatures. The activation energies of the complexed films were calculated from the dielectric loss tangent spectra and were found to be 0.35, 0.30, 0.27 and 0.28 eV. The cyclic voltammogram (CV) curves of (PVA: LiFePO4) (75:25)+PC film exhibited higher specific capacities than those for other films.  相似文献   

10.
A comb‐like polyether, poly(3‐2‐[2‐(2‐methoxyethoxy)ethoxy]ethoxymethyl‐3′‐methyloxetane) (PMEOX), was reacted with hexamethylene diisocyanate and extended with butanediol in a one‐pot procedure to give novel thermoplastic elastomeric poly(ether urethane)s (TPEUs). The corresponding hybrid solid polymer electrolytes were fabricated through doping a mixture of TPEU and poly(vinylidene fluoride) with three kinds of lithium salts, LiClO4, LiBF4 and lithium trifluoromethanesulfonimide (LiTFSI), and were characterized using differential scanning calorimetry, thermogravimetric analysis and Fourier transform infrared spectroscopy. The ionic conductivity of the resulting polymer electrolytes was then assessed by means of AC impedance measurements, which reached 2.1 × 10?4 S cm?1 at 30 °C and 1.7 × 10?3 S cm?1 at 80 °C when LiTFSI was added at a ratio of O:Li = 20. These values can be further increased to 3.5 × 10?4 S cm?1 at 30 °C and 2.2 × 10?3 S cm?1 at 80 °C by introducing nanosized SiO2 particles into the polymer electrolytes. Copyright © 2006 Society of Chemical Industry  相似文献   

11.
Summary   A new class of lithium salt with single-ionic characteristics, lithium sulfonated styrene oligomer (LiSSO) [(CH2CHC6H5)7-(CH2CHC6H4SO3 Li+)2], was synthesized and its complex with poly(ethylene oxide) (PEO) was prepared. The maximum ionic conductivity of the PEO/LiSSO complex at 65°C was 2.1×10−4S/cm at a salt concentration of [Li+]/[EO] = 0.20. The lithium cationic transference number (t +) of the PEO/LiSSO complex was found to be 0.95, and the polymer electrolyte was electrochemically stable up to 6.2V. Received: 2 April 2001/Revised version: 30 July 2001/Accepted: 30 July 2001  相似文献   

12.
The recently developed technique of cold sintering process (CSP) enables densification of ceramics at low temperatures, i.e., <300°C. CSP employs a transient aqueous solvent to enable liquid phase‐assisted densification through mediating the dissolution‐precipitation process under a uniaxial applied pressure. Using CSP in this study, 80% dense Li1.5Al0.5Ge1.5(PO4)3 (LAGP) electrolytes were obtained at 120°C in 20 minutes. After a 5 minute belt furnace treatment at 650°C, 50°C above the crystallization onset, Li‐ion conductivity was 5.4 × 10?5 S/cm at 25°C. Another route to high ionic conductivities ~10?4 S/cm at 25°C is through a composite LAGP ‐ (PVDF‐HFP) co‐sintered system that was soaked in a liquid electrolyte. After soaking 95, 90, 80, 70, and 60 vol% LAGP in 1 M LiPF6 EC‐DMC (50:50 vol%) at 25°C, Li‐ion conductivities were 1.0 × 10?4 S/cm at 25°C with 5 to 10 wt% liquid electrolyte. This paper focuses on the microstructural development and impedance contributions within solid electrolytes processed by (i) Crystallization of bulk glasses, (ii) CSP of ceramics, and (iii) CSP of ceramic‐polymer composites. CSP may offer a new route to enable multilayer battery technology by avoiding the detrimental effects of high temperature heat treatments.  相似文献   

13.
Orthorhombic Sc2Mo3O12 films have been successfully prepared via spin coating technique followed by annealing at 500–750 °C. The phase composition, microstructure, morphology and negative thermal behavior of the synthesized Sc2Mo3O12 films were investigated. XRD and XPS analysis indicate that as-deposited film is amorphous. Orthorhombic Sc2Mo3O12 films can be prepared after post-annealing at 500–750 °C for 1 h. The crystallinity of Sc2Mo3O12 films gradually improved with the increase of post-annealing temperature. SEM analysis shows as-deposited film is smooth and compact, and the grain size of Sc2Mo3O12 film grows up as the post-annealing temperature increases. Variable temperature XRD analysis demonstrates that the synthesized orthorhombic Sc2Mo3O12 films show stable thermo-chemical and anisotropic NTE property in 25–700 °C. The corresponding coefficients of thermal expansion (CTEs) of the orthorhombic Sc2Mo3O12 film in a, b and c directions are ?6.68 × 10?6 °C?1, 5.08 × 10?6 °C?1 and ?4.76 × 10?6 °C?1, respectively. The whole unit cell of the orthorhombic Sc2Mo3O12 film shrinks and the volumetric CTE of the Sc2Mo3O12 thin film is ?6.36 × 10?6 °C?1, and the linear CTE is about ?2.12 × 10?6 °C?1 (αv = 3αl).  相似文献   

14.
《Ceramics International》2023,49(5):7935-7945
Solid polymer electrolytes (SPEs) have attracted much attention because of their potential in improving energy density and safety. Vanadium doped ceramic matrix Li6.7La3Zr1.7V0.3O12 (LLZVO) was synthesized by high-temperature annealing, and formed a composite electrolyte with polyethylene oxide (PEO). Compared with pure PEO electrolyte membrane, the composite electrolyte membrane exhibited better ionic conductivity (30 °C: 3.2 × 10?5 S cm?1; 80 °C: 3.6 × 10?3 S cm?1). The combination of LLZVO was beneficial to improve the lithium ion transference number (tLi+) of SPE, which was as high as 0.81. The Li/SPE/LiFePO4 battery shows good cycling ability, with a specific capacity of 142 mAh g?1 after a stable cycle of 150 cycles. Meanwhile, the symmetrical lithium battery with composite electrolyte can work continuously for 1200 h without short circuit at the current density of 0.1 mA cm?2 at 50 °C, and the capacity is 0.176 mAh. Vanadium doped ceramic matrix LLZVO as an active ionic conductor, improved the overall performance of solid electrolyte.  相似文献   

15.
Lithium-sulfur (Li–S) batteries are attractive due to their high theoretical energy density. However, conventional Li–S batteries with liquid electrolytes undergo polysulfide shuttle-effect and lithium dendrite formation during charge/discharge process, leading to poor electrochemical performance and safety issues. Garnet type Li7La3Zr2O12 (LLZO) solid-state electrolyte (SSE) restricts the penetration of polysulfides and exhibits high ionic conductivity at room temperature (RT). Herein, Li6.5La3Zr1.5Nb0.5O12 (LLZNO) ceramic electrolyte using Li3PO4 (LPO) as sintering aids (LLZNO-LPO) is prepared by the rapid sintering method and is applied to construct a shuttle-effect free solid-state Li–S battery. The SSE displays high conductive pure cubic-LLZO phase; during the rapid sintering, LPO melts and junctions the voids between the grains, thus improves Li+ conductivity. As a result, the LLZNO-LPO ceramic electrolyte with Li+ conductivity of 4.3 × 10?4 S cm?1 and high critical current density (CCD) of 1.2 mA cm?2 is obtained at RT. The Li–S solid-state battery which utilizes LLZNO-LPO ceramic electrolyte can deliver an initial discharge capacity of 943 mA h·g?1 and 602 mA h·g?1 retention after 60 cycles. In the same time, the initial coulombic efficiency is as high as 99.5%, indicating that the SSE can effectively block the polysulfide shuttle towards the Li anode and fulfill a shuttle-free Li–S battery.  相似文献   

16.
Li1.4Al0.4Ti1.6(PO4)3 (LATP) was synthesized using a glass‐ceramics approach through crystallization in a conventional box furnace and a modified microwave furnace. The microstructure of samples that were microwave processed at 1000°C showed a larger average grain size (0.87 μm) when compared with the grain size of conventionally processed samples (0.30 μm) at the same temperature. Microwave processing led to significant enhancement of the conductivity when compared with conventional processing for all crystallization temperatures investigated. The highest total conductivity achieved was of glass microwave processed at 1000°C, with a conductivity of 5.33 × 10?4 S/cm. This conductivity was five times higher than that of LATP crystallized conventionally at the same temperature.  相似文献   

17.
《Ceramics International》2022,48(18):25949-25957
The design and regulation of the ion transport channels in the polymer electrolyte is an important means to improve the lithium ion transport behavior of the electrolyte. In this work, we for the first time combined the high ionic conductive inorganic ceramic electrolyte Li1.5Al0.5Ge1.5(PO4)3 (LAGP) with flexible polypropylene oxide (PPO) polymer electrolyte to synthesize a high-filling LAGP/PPO composite solid electrolyte film and regulated the ion transport channels from ‘Ceramics-in-Polymer’ mode to ‘Polymer-in-Ceramics' mode by optimizing the ratio of LAGP vs. PPO. The results reveal that when the LAGP content <40%, the electrolyte belongs to ‘LAGP-in-PPO’, and then changes to ‘PPO-in-LAGP’ when the LAGP content exceeds 40%. Compared with ‘LAGP-in-PPO’, the ‘PPO-in-LAGP’ shows better comprehensive properties, especially for the 75% LAGP-filled PPO electrolyte, the room-temperature ionic conductivity is as high as 3.46 × 10?4 Scm?1, the ion migration number and voltage stable window reach 0.83 and 4.78 V respectively. This high-filled composite electrolyte possesses high tensile stress of 40 MPa with a strain of 46% and withstands working environment up to 200 °C. The NCM622/Li solid-state battery composed of this electrolyte also presents good rate and cycle performances with a capacity retention of 80% after 230 cycles at 0.3C because of its high ion transport capability and good inhibition of lithium dendrites. This composite structural design is expected to develop high-performance solid-state electrolytes suitable for high-voltage solid-state lithium batteries.  相似文献   

18.
Lithium garnet‐type oxides Li7?2xLa3Zr2?xMoxO12 (x=0, 0.1, 0.2, 0.3) ceramics were prepared by a sol‐gel method. The influence of molybdenum on the structure, microstructure and conductivity of Li7La3Zr2O12 were investigated by X‐ray diffraction, scanning electron microscopy, and impedance spectroscopy. The cubic phase Li7La3Zr2O12 has been stabilized by partial substitution of Mo for Zr at low temperature. The introduction of Mo (x≥0.1) can accelerate densification. Li6.6La3Zr1.8Mo0.2O12 sintered at lower temperature 1100°C for 3 hours exhibits highest total ionic conductivity of 5.09 × 10?4 S/cm. Results indicate that the Mo doping LLZO synthesized by sol‐gel method effectively lowers its sintering temperature and improves the ionic conductivity.  相似文献   

19.
The transparent and flexible solid polymer electrolytes (SPEs) were fabricated from polyacrylonitrile‐polyethylene oxide (PAN‐PEO) copolymer which was synthesized by methacrylate‐headed PEO macromonomer and acrylonitrile. The formation of copolymer is confirmed by Fourier‐transform infrared spectroscopy (FTIR) measurements. The ionic conductivity was measured by alternating current (AC) impedance spectroscopy. Ionic conductivity of PAN‐PEO‐LiClO4 complexes was investigated with various salt concentration, temperatures and molecular weight of PEO (Mn). And the maximum ionic conductivity at room temperature was measured to be 3.54 × 10?4 S/cm with an [Li+]/[EO] mole ratio of about 0.1. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 461–464, 2006  相似文献   

20.
NaSICON-type lithium conductor Li1.3Al0.3Ti1.7(PO4)3 (LATP) is synthesized with controlled grain size and composition using solution chemistry. After thermal treatment at 850 °C, sub-micronic crystallized powders with high purity are obtained. They are converted into ceramic through Spark Plasma Sintering at 850–1000 °C. By varying the processing parameters, pellet with conductivities up to 1.6 × 10?4 S/cm with density of 97% of the theoretical density have been obtained. XRD, FEG-SEM, ac-impedance and Vickers indentation were used to characterize the products. The influence of sintering parameters on pellet composition, microstructure and conductivity is discussed in addition to the analysis of the mechanical behavior of the grains interfaces.  相似文献   

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