通过有效掺入氯化锂提高石榴石 Li7La3Zr2O12 电解质的电化学性能

IF 5.1 2区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Ceramics International Pub Date : 2024-10-02 DOI:10.1016/j.ceramint.2024.10.015

Yali Luo , Jiaxin Dong , Yuanjun Wang , Zhaoqi Wang , Zi'ang Chen , He Zhang

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引用次数: 0

摘要

石榴石型掺杂Ta的Li7La3Zr2O12（LLZO）锂离子传导陶瓷电解质具有良好的锂+传导性、对金属锂正极的稳定性以及在环境空气中制备的可行性，已成为开发高能量密度全固态锂电池的重要候选材料。为了进一步提高 LLZO 的锂离子电导率，使其与商用有机液态电解质相媲美，本文有效地引入了氯化锂（LiCl），通过高温煅烧工艺合成了标称成分为 (Li6.5La3Zr1.5Ta0.5O12)1-x-(LiCl)x （x = 0、5mol%、10mol%、15mol%、20mol% 和 25mol%）的石榴石型陶瓷电解质。通过 X 射线衍射测量和拉曼光谱分析，确认了具有高导电性能的立方结构。配备能量色散光谱仪的场发射扫描电子显微镜和密度测定也能观察到结构信息。在上述研究的陶瓷成分中，制备的 (Li6.5La3Zr1.5Ta0.5O12)0.85-(LiCl)0.15 陶瓷电解质片在 1200 °C 下烧结 12 小时后，通过交流阻抗分析得出室温锂离子电导率为 1.22 × 10-3 S-cm-1，并通过阿伦尼乌斯方程计算得出相应的活化能为 0.262eV。此外，还通过直流极化进行了电子电导率测量，以确认所有研究陶瓷的离子性质。此外，锂硫（Li|(Li6.5La3Zr1.5Ta0.5O12)0.85-(LiCl)0.15 |Li）对称电池具有 92.3 Ω cm2 的小界面电阻，并能在室温下以 0.1 mA cm-2 的电流稳定运行 1000 h 而不发生短路。采用(Li6.5La3Zr1.5Ta0.5O12)0.85-(LiCl)0.15电解质的杂化锂硫电池在0.1C和0.2C的电流密度下，室温初始放电容量分别达到1204mAh-g-1和1152 mAh-g-1，具有极高的库仑效率和循环稳定性。此外，锂硫电池还能在不同电流密度下表现出优异的循环性能和良好的容量恢复能力。上述研究结果表明，在Li6.5La3Zr1.5Ta0.5O12电解质中加入低熔点氯化锂是合成立方致密锂质石榴石陶瓷片的有效方法，可用于高性能可充电下一代固态电池。

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Enhanced electrochemical performance of garnet Li7La3Zr2O12 electrolyte by efficient incorporation of LiCl

Garnet-type Ta-doped Li₇La₃Zr₂O₁₂ (LLZO) lithium-ion-conducting ceramic electrolytes has become the promising and critical candidate for developing the high-energy-density all-solid-state lithium batteries, due to the satisfied Li⁺ conductivity, stability against metallic lithium anode, and the feasible preparation under ambient air. Here, to further increase the lithium-ion conductivity of LLZO comparable to that of the commercial organic liquid electrolytes, lithium chloride (LiCl) is effectively introduced to synthesize the garnet-type ceramic electrolytes with the nominal composition (Li_6.5La₃Zr_1.5Ta_0.5O₁₂)_1-x–(LiCl)_x (x = 0, 5mol%, 10mol%, 15mol%, 20mol%, and 25mol%) via high-temperature calcination process. The cubic structure with highly conductive performance is confirmed from X-ray diffraction measurement as well as Raman spectra analysis. Structural information is observed according to field emission scanning electron microscope equipped with energy dispersive spectrometer and density measurements. Among above investigated ceramic compositions, the prepared (Li_6.5La₃Zr_1.5Ta_0.5O₁₂)_0.85–(LiCl)_0.15 ceramic electrolyte sheet sintered at 1200 °C for 12h presents the room-temperature Li-ion conductivity of 1.22 × 10⁻³ S·cm⁻¹ by alternating current (AC) impedance analysis along with the corresponding activation energy of 0.262eV through Arrhenius equation calculation. The electronic conductivity measurements are also done by direct-current polarization to confirm the ionic nature for all investigated ceramics. Furthermore, the Li|(Li_6.5La₃Zr_1.5Ta_0.5O₁₂)_0.85–(LiCl)_0.15 |Li symmetric batteries can possess the small interfacial resistance of 92.3 Ω cm² and stably run for 1000 h at 0.1 mA cm⁻² without a short circuit at room temperature. The hybridized lithium-sulfur battery with (Li_6.5La₃Zr_1.5Ta_0.5O₁₂)_0.85–(LiCl)_0.15 electrolyte delivered excellent initial room-temperature discharge capacity of 1204mAh·g⁻¹ and 1152 mAh·g⁻¹ under the current density of 0.1C and 0.2C respectively, large coulombic efficiency, and great cycling stability. Moreover, the lithium-sulfur batteries also can show excellent cycling performances under different current densities and a good capacity recoverability. The above investigation results suggest that the low-melting-point LiCl incorporation in Li_6.5La₃Zr_1.5Ta_0.5O₁₂ electrolyte is an effective measurement to synthesize the cubic and dense Li-stuff garnet ceramic sheets for the high-performance rechargeable next-generation solid-state batteries.

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来源期刊

Ceramics International 工程技术-材料科学：硅酸盐

CiteScore

9.40

自引率

15.40%

发文量

4558

审稿时长

25 days

期刊介绍： Ceramics International covers the science of advanced ceramic materials. The journal encourages contributions that demonstrate how an understanding of the basic chemical and physical phenomena may direct materials design and stimulate ideas for new or improved processing techniques, in order to obtain materials with desired structural features and properties. Ceramics International covers oxide and non-oxide ceramics, functional glasses, glass ceramics, amorphous inorganic non-metallic materials (and their combinations with metal and organic materials), in the form of particulates, dense or porous bodies, thin/thick films and laminated, graded and composite structures. Process related topics such as ceramic-ceramic joints or joining ceramics with dissimilar materials, as well as surface finishing and conditioning are also covered. Besides traditional processing techniques, manufacturing routes of interest include innovative procedures benefiting from externally applied stresses, electromagnetic fields and energetic beams, as well as top-down and self-assembly nanotechnology approaches. In addition, the journal welcomes submissions on bio-inspired and bio-enabled materials designs, experimentally validated multi scale modelling and simulation for materials design, and the use of the most advanced chemical and physical characterization techniques of structure, properties and behaviour. Technologically relevant low-dimensional systems are a particular focus of Ceramics International. These include 0, 1 and 2-D nanomaterials (also covering CNTs, graphene and related materials, and diamond-like carbons), their nanocomposites, as well as nano-hybrids and hierarchical multifunctional nanostructures that might integrate molecular, biological and electronic components.