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1.
《Ceramics International》2020,46(6):7634-7641
In this paper, the microstructure and ionic conductivity of Li1.5Al0.5Ge1.5(PO4)3 (LAGP) solid electrolytes prepared by spark plasma sintering (SPS) were investigated by XRD, SEM, TEM and EIS, respectively. The results showed that as the sintering temperature was increased, both the relative density and the ionic conductivity of the sintered LAGP samples first increased and then decreased, achieving a maximum value of 97% and 2.12 × 10−4 S cm−1 simultaneously at 700 °C. At the same time, the crystallinity of the sintered samples was improved, while a few impurity phases, such as AlPO4 and GeO2, appeared in the samples. It was also found that carbon contamination and oxycarbide gas was be brought in during SPS. Carbon contamination could produce an extra grain boundary impedance to the samples and could be removed by annealing at 500 °C in an air atmosphere. Oxycarbide gas could affect the relative density of the sintered LAGP samples and could be mitigated by choosing a suitable SPS process. Moreover, the shear modulus of the sintered LAGP was measured to be 49.6 GPa, which exceeded the minimum value of 8.5 GPa that was necessary to suppress Li dendrite growth. 相似文献
2.
Seth S. Berbano Jing Guo Hanzheng Guo Clive A. Randall 《Journal of the American Ceramic Society》2017,100(5):2123-2135
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
3.
Nurbol Tolganbek Yerkezhan Yerkinbekova Alimzhan Khairullin Zhumabay Bakenov Kiyoshi Kanamura Almagul Mentbayeva 《Ceramics International》2021,47(13):18188-18195
Increasing demand for safe energy storage and portable power sources has led to intensive investigation for all-solid state Li-ion batteries and particularly to solid electrolytes for such rechargeable batteries. One of the most promising types of solid electrolytes is NASICON-structured Li1.3Al0.3Ti1.7(PO4)3 (LATP) due to its relatively high ionic conductivity and stability towards air and moisture. Here, the work is aimed on implementing the steps to hinder formation of impurity phases reported for various synthesis routes. Consequently, the applied modifications in the preparation strategies alter a crystal shape and size of prepared material. These two parameters have an enormous impact on properties of LATP. Fabrication of larger particles with a cubic shape significantly improves its ionic conductivity. As a result, LATP preparation methods such as a solution chemistry and molten flux resulted in the highest ionic conductivity samples with the value of ~10?4 S cm?1 at room temperature. Other LATPs obtained by solid-state reaction, sol-gel and spray drying methods depicted the ionic conductivity of ~10?5 S cm?1. The activation energy of lithium ion transfer in LATP varied in a range of 0.25–0.4 eV, which is in well agreement with the previously reported data. 相似文献
4.
Kun Yu Ye Tian Rui Gu Li Jin Ruiping Ma Hongchen Sun Youlong Xu Zhuo Xu Xiaoyong Wei 《Journal of the European Ceramic Society》2018,38(13):4483-4487
Perovskite-type solid electrolyte lanthanum lithium titanate (LLTO), exhibiting high intrinsic ionic conductivity, has been attracting interests because of its potential use in all solid-state lithium-ion batteries. In this work, we prepared LLTO ceramics by solid state reaction method and studied their conductivity and dielectric properties systematically. It is found that the bulk conductivity of LLTO is several orders of magnitude higher than the grain boundary conductivity. In addition, colossal permittivity was observed in LLTO ceramics in wide frequency/temperature ranges. Two non-Debye type relaxation peaks were observed in the imaginary part of permittivity, resulting from Li+ ions motion and accumulation near interfaces of grains/grain boundaries/electrodes. It is suggested that colossal permittivity may originate from the lithium ion dipoles inside the samples and the interfacial polarization of lithium ion accumulation near the grain boundaries. These results clarify the relations among colossal permittivity, relaxation behavior and ionic conduction in solid ion conductor ceramics. 相似文献
5.
《Journal of the European Ceramic Society》2023,43(14):6170-6179
A novel approach is proposed to design high-quality NASICON–type solid-state electrolytes (SSEs) based on Li1.3Al0.3Ti1.7(PO4)3 (LATP) by incorporating nanoparticles into a matrix of microparticles, which could efficiently improve densification of LATP SSEs by sintering. Moreover, LATP SSEs with bimodal microstructures are obtained by tuning mass ratio of 60 nm and 600 nm ceramic particles, which are fabricated by sol-polymer and molten quenching methods, respectively. The LATP SSE containing 60 nm and 600 nm particles with the mass ratio of 10%/90% displays a high ionic conductivity of (5.93 ± 0.24)× 10−4 S/cm at room temperature and relative density of 95.5 ± 1.1% after sintering at 900 °C for 6 h. Besides, the Li||LATP||Li symmetric cell with the mass ratio of 10%/90% exhibits better cyclic stability with a steady polarization voltage of 121.2 mV than that of other ratios. Therefore, SSEs with multimodal microstructures pave a promising venue for practical application of high-energy-density and safe solid-state Li metal battery. 相似文献
6.
J. Pierce Robinson Padmakar D. Kichambare Jay L. Deiner Ryan Miller Michael A. Rottmayer Gary M. Koenig Jr 《Journal of the American Ceramic Society》2018,101(3):1087-1094
All‐solid‐state lithium‐ion electrolytes offer substantial safety benefits compared to flammable liquid organic electrolytes. However, a great challenge in solid electrolyte batteries is forming a stable and ion conducting interface between the electrolyte and active material. This study investigates and characterizes a possible solid‐state electrode‐electrolyte pair for the high voltage active cathode material LiMn1.5Ni0.5O4 (LMNO) and electrolyte Li1+xAlxGe2‐x(PO4)3 (LAGP). In situ X‐ray diffraction measurements were taken on pressed pellets comprised of a blend of LMNO and LAGP during exposure to elevated temperatures to determine the product materials that form at the interface of LMNO and LAGP and the temperatures at which they form. In particular, above 600°C a material consistent with LiMnPO4 was formed. Scanning electron microscopy and energy‐dispersive X‐ray spectroscopy were used to image the morphology and elemental compositions of product materials at the interface, and electrochemical characterization was performed on LMNO‐coated LAGP electrolyte pellet half cells. Although the voltage of Li/LAGP/LMNO assembled batteries was promising, thick interfacial phases resulted in high electrochemical resistance, demonstrating the need for further understanding and control over material processing in the LAGP/LMNO system to reduce interfacial resistance and improve electrochemical performance. 相似文献
7.
《Ceramics International》2017,43(15):11879-11884
Li6.5La3Zr1.5Nb0.5O12 (LLZN) garnet-type structure was synthesized at low temperature with B2O3 addition by solid state reaction method. The effects of B2O3 content on the formation, microstructure, ionic conductivity and activation energy of the LLZN solid electrolytes have been investigated by X-Ray diffraction (XRD), scanning electron microscopy (SEM) and alternate current (AC) impedance spectroscopy. The cubic LLZN phase was obtained after calcining at 850 °C for 6 h and no phase evolution was observed after sintering at 1100 °C for 6 h. The relative density and lithium ion conductivity increased first and then decreased with increasing B2O3 content, reaching the maximum value of 92.4% and 1.86×10−4 S cm−1 respectively in the sample with 1.4 wt% B2O3. By contrast, the activation energy reached a minimum value of ~31.5 kJ mol−1. 相似文献
8.
《Journal of the European Ceramic Society》2020,40(5):1975-1982
Free-standing Li1.5Al0.5Ti1.5P3O12 electrolyte sheets with a thickness of 50–150 μm were prepared by tape casting followed by sintering at 850–1000 °C in air. While a sintering temperature of 850 °C was too low to achieve appreciable densification and grain growth, a peak relative density of 95% was obtained at 920 °C. At higher sintering temperatures, the microstructure changed from a bimodal grain size distribution towards exclusively large grains (> 10 μm), accompanied by a decrease in relative density (down to 86% at 1000 °C). In contrast, ionic conductivity increased with increasing sintering temperature, from 0.1 mS/cm at 920 °C to 0.3 mS/cm at 1000 °C. Sintering behavior was improved by adding 1.5% of amorphous silica to the slurry. In this way, almost full densification (99.8%) and an ionic conductivity of 0.2 mS/cm was achieved at 920 °C.Mechanical characterization was carried out on the almost fully densified material, yielding elastic modulus and hardness values of 109 and 8.7 GPa, respectively. The fracture strength and Weibull modulus were also characterized. The results confirm that densification and reduction of grain size improve the mechanical properties. 相似文献
9.
采用溶胶-凝胶法合成Li1.3Al0.3Ti1.7(PO4)3粉末,向Li1.3Al0.3Ti1.7(PO4)3粉末中添加不同摩尔分数的Li3PO4助熔剂烧结制备锂离子固体电解质Li1.3Al0.3Ti1.7(PO4)3烧结片。通过X射线衍射仪、扫描电子显微镜研究合成产物的结构与形貌,采用循环伏安及交流阻抗技术研究合成产物的氧化-还原电位、离子电导率和活化能。结果表明,添加与未添加Li3PO4助熔剂的Li1.3Al0.3Ti1.7(PO4)3烧结片具有相似的X射线衍射结果。添加Li3PO4的Li1.3Al0.3Ti1.7(PO4)3烧结片空隙率较小,更为致密。添加Li3PO4对Li1.3Al0.3Ti1.7(PO4)3的氧化-还原电位影响不大。在所有添加Li3PO4助熔剂的Li1.3Al0.3Ti1.7(PO4)3烧结片中,添加摩尔分数1%Li3PO4的烧结片具有最高的离子电导率6.15×10-4S.cm-1和最低的活化能0.314 2 eV。 相似文献
10.
Lin Yang Hong Zhang Jiahao Chen Hongzhu Chen Zhicheng Li 《Ceramics International》2021,47(13):17950-17955
All-solid-state Li-ion batteries (LIBs) have recently attracted widespread attention for their high energy density and safety. Some research have conducted on the Li2ZrO3-based Li-ion conductor electrolytes, while there is little work on the conductivity below 100 °C, although it is very important for LIBs work around room temperature. Here, monoclinic Li2ZrO3-based ceramics are prepared via a wet chemistry method, and the conductivities of Li2ZrO3 ceramics are tuned by defect engineering of Al3+ ions introduction. The conductivity of Al-doped Li2ZrO3 reaches up to 3.06 × 10-4 S cm-1 at 25 °C, the related activation energy of conduction is less than 0.1 eV. Simulation calculation using bond valence site energy reveals that there is a two-dimensional Li-ion migration network in the crystal structure of Li2ZrO3. 相似文献
11.
《Ceramics International》2022,48(1):157-163
NASICON-type structured compounds Li1+xMxTi2-x(PO4)3 (M = Al, Fe, Y, etc.) have captured much attention due to their air stability, wide electrochemical window and high lithium ion conductivity. Especially, Li1.3Al0.3Ti1.7(PO4)3 (LATP) is a potential solid electrolyte due to its high ionic conductivity. However, its actual density usually has a certain gap with the theoretical density, leading the poor ionic conductivity of LATP. Herein, LATP solid electrolyte with series of SnO–P2O5–MgO (SPM, 0.4 wt%, 0.7 wt%, 1.0 wt%, 1.3 wt%) glass addition was successfully synthesized to improve the density and ionic conductivity. The SPM addition change Al/Ti–O bond and P–O bond distances, leading to gradual shrinkage of octahedral AlO6 and tetrahedral PO4. The bulk conductivity of the samples increases gradually with SPM glass addition from 0.4 wt% to 1.3 wt%. Both SPM and the second-phase LiTiPO5, caused by glass addition, are conducive to the improvement of compactness. The relative density of LATP samples increases first from 0 wt% to 0.7 wt%, and then decreases from 0.7 wt% to 1.3 wt% with SPM glass addition. The grain boundary conductivity also changes accordingly. Especially, the highest ionic conductivity of 2.45 × 10?4 S cm?1, and a relative density of 96.72% with a low activation energy of 0.34 eV is obtained in LATP with 0.7 wt% SPM. Increasing the density of LATP solid electrolyte is crucial to improve the ionic conductivity of electrolytes and SPM glass addition can promote the development of dense oxide ceramic electrolytes. 相似文献
12.
Jinghua Wu Milad Kermani Lei Cao Bohan Wang Zhiquan Dai Le Fu Chunfeng Hu Salvatore Grasso 《International Journal of Applied Ceramic Technology》2023,20(4):2125-2130
Lithium aluminum germanium phosphate solid electrolyte is a promising candidate for all-solid-state batteries. The currently available processing techniques based on melting-quenching require a rather lengthy crystallization step lasting up to 8 hours. In this work, the newly emerged ultra-fast high-temperature sintering (UHS) was proposed to achieve in a single step reactive consolidation of powder mixture (GeO2, Al(PO3)3, LiPO3) and crystallization of the electrolyte within 16 minutes. Samples produced using UHS had a better phase purity, reduced Li loss, and improved ionic conductivity when compared to the counterparts prepared using conventional crystallization at 850°C for 6 h. In fact, specimens prepared by UHS achieved a crystallinity of 90% and ionic conductivity as high as 1.31 × 10−4 S cm−1. 相似文献
13.
《Journal of the European Ceramic Society》2022,42(3):1023-1032
Li-ion batteries (LIBs) are the ubiquitous technology to power portable electronics; however, for the next-generation of high-performing electrochemical energy storage systems for electric vehicles and smart grid facilities, breakthroughs are needed, particularly in the development of solid-state electrolytes, which may allow for enhanced energy density while enabling lithium metal anodes, combined with unrivalled safety and operative reliability. In this respect, here we present the successful synthesis of a glass-ceramic Li1.4Al0.4Ge0.4Ti1.4(PO4)3 NASICON-type solid-state electrolyte (SSE) through a melt-casting technique. Being grain boundaries crucial for the total ionic conductivity of SSEs, the effect of the addition of diboron trioxide (B2O3, 0.05 wt.%) to promote their liquefaction and restructuring is investigated, along with the effects on the resulting microstructures and ionic conductivities. By the thorough combination of structural-morphological and electrochemical techniques, we demonstrate that bulk materials show improved performance compared to their powder sintered counterpart, achieving remarkable ion mobility (> 0.1 mS cm–1 at –10 °C) and anodic oxidation stability (> 4.8 V vs Li+/Li). The addition of B2O3 positively affects the grain cohesion and growth, thus reducing the extension of the grain boundaries (and the related grain/grain interface resistance) and, therefore, increasing the overall ion mobility. In addition, B2O3 is seen to contrast the microcracks formation in the LAGTP system under study which, overall, shows very promising prospects as SSE for the next-generation of high-energy density, safe lithium-based batteries. 相似文献
14.
Igor d'Anciães Almeida Silva Adriana M. Nieto-Muñoz Ana Candida M. Rodrigues Hellmut Eckert 《Journal of the American Ceramic Society》2020,103(7):4002-4012
This work reports structural and lithium-ion mobility studies in NASICON single- or multiple phase Li1+xMxGe2−x(PO4)3 (M = Ga3+, Sc3+, Y3+) glass-ceramics using solid-state NMR techniques, X-ray powder diffraction, and impedance spectroscopy. X-ray powder diffraction data show the successful incorporation of Ga3+ and Sc3+ into the Ge4+ octahedral sites of the NASICON structure at the levels of x = 0.5 and 0.4, respectively. The glass-to-crystal transition was further characterized by multinuclear NMR and electrical conductivity measurements. Among the studied samples, the gallium-containing glass-ceramic presented the highest DC conductivity, 1.1 × 10−4 S/cm at room temperature, whereas for the Sc-containing samples, the maximum room temperature conductivity that could be reached was 4.8 × 10−6 S/cm. No indications of any substitution of Ge4+ by Y3+ could be found. 相似文献
15.
16.
Xiao Huang Jianmeng Su Zhen Song Tongping Xiu Jun Jin Michael E. Badding Zhaoyin Wen 《Ceramics International》2021,47(2):2123-2130
Garnet-type Li7La3Zr2O12 (LLZO) Li+ ion solid electrolyte is a promising candidate for next generation high-safety solid-state batteries. Ga-doped LLZO exhibits excellent Li+ ion conductivity, higher than 1 × 10?3 S cm?1. In this research, the doping amount of Ga, the calcination temperature of Ga-LLZO primary powders, the sintering conditions and the evolution of grains are explored to demonstrate the optimum parameters to obtain a highly conductive ceramics reproducibly via conventional solid-state reaction methods under ambient air sintering atmosphere. Cubic LLZO phase is obtained for Li6.4Ga0.2La3Zr2O12 powder calcined at low temperature 850 °C. In addition, ceramic pellets sintered at 1100 °C for 320 min using this powder have relative densities higher than 94% and conductivities higher than 1.2 × 10?3 S cm?1 at 25 °C. 相似文献
17.
《Ceramics International》2022,48(4):5035-5039
In this work, the Al doped high entropy perovskite Li0.2La0.2Ca0.2Sr0.2Ba0.2TiO3 ceramic is synthesized by using a solid state reaction method, and the effect of different doping amount on the crystal structures and conductivity are also studied. The result proves that doping leads to a positive influence on the conductivity of ceramic. The material of Li0.1(LiLaCaSrBa)Ti0.9Al0.1O3 (LLCSBTA-0.1) exhibits a high total conductivity with approximately 3.92 × 10-7 S cm-1 at 30 °C and an activation energy of 0.39 eV. The beneficial result can be ascribed to the increase of Li + concentration. The Li0.2La0.2Ca0.2Sr0.2Ba0.2TiO3 presents a pure cubic perovskite structure, but with partial tetragonal structure due to the addition of Al2O3. However, these high entropy perovskite ceramics showed porous structures which are unfavourable for lithium ion conduction. The electrochemical property of the Li0.1(LiLaCaSrBa)Ti0.9Al0.1O3 as electrode is investigated as well. The results show that the Li0.1(LiLaCaSrBa)Ti0.9Al0.1O3 electrode exhibits good cyclability and stability for the insert-extraction of lithium ions with the specific capacity of 58.6 mA h g?1. 相似文献
18.
Structural and electrical properties of ceramic Li-ion conductors based on Li1.3Al0.3Ti1.7(PO4)3-LiF
《Journal of the European Ceramic Society》2020,40(1):85-93
The work presents the investigations of Li1.3Al0.3Ti1.7(PO4)3-xLiF Li-ion conducting ceramics with 0 ≤ x ≤ 0.3 by means of X-ray diffractometry (XRD), 7Li, 19F, 27Al and 31P Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy, thermogravimetry (TG), scanning electron microscopy (SEM), impedance spectroscopy (IS) and density method. It has been shown that the total ionic conductivity of both as-prepared and ceramic Li1.3Al0.3Ti1.7(PO4)3 is low due to a grain boundary phase exhibiting high electrical resistance. This phase consists mainly of berlinite crystalline phase as well as some amorphous phase containing Al3+ ions. The electrically resistant phases of the grain boundary decompose during sintering with LiF additive. The processes leading to microstructure changes and their effect on the ionic properties of the materials are discussed in the frame of the brick layer model (BLM). The highest total ionic conductivity at room temperature was measured for LATP-0.1LiF ceramic sintered at 800 °C and was equal to σtot = 1.1 × 10−4 S cm−1. 相似文献
19.
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
20.
以固相法合成固体电解质Li1.3Al0.3Ti1.7(PO4)3(LATP)粉末。研究了烧结温度以及烧结时间对LATP离子电导率的影响。采用X射线衍射、扫描电子显微镜和交流阻抗技术对材料粉末以及烧结片相组成、结构和离子导电性进行表征。结果表明,900℃条件下合成的粉末为纯相LATP,颗粒均匀,当LATP电解质基片在900℃下烧结4 h,得到的LATP烧结片表面致密光滑,而且离子电导率较高,为3.03×10-4S/cm。 相似文献