APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING
·
2018
·Vol. 124
·期 6
·1-8
·
IF 1.604
Lin Changwei,Tang Yu,Song Jun,Han Lei,Yu Jingbo,Lu Anxian
In the present study, series of garnet-type Li 6.75+ x La 3− x Sr
x
Zr 1.75 Nb 0.25 O 12 solid electrolytes [LLSZN with various Sr contents ( x = 0.05–0.25)] have been prepared via conventional solid-state method. The effects of Sr contents on their phase structure and ionic conductivity have been systematically investigated on the combined measurements of X-ray diffraction and scanning electron microscopy and alter current impedance spectroscopy. Our results reveal that a phase transition from tetragonal to cubic structure occurs when both Sr and Nb elements is introduced, and such a cubic structure can be stable over the whole Sr contents variation, which is suggested to provide a beneficial impact on the performance of LLSZN. Accordingly, both relative density and total ionic conductivity exhibit a favorable tendency of increasing first and then decreasing with increased Sr contents, wherein a peak value at 93.46% and 5.09 × 10 −4 S cm −1 , respectively, can be well achieved. Particularly, the maximum ionic conductivity is almost twice that of the compared sample (2.93 × 10 −4 S cm −1 ), and possess the minimum activation energy ~ 0.30 eV. Such a modification method, featured with higher efficiency and lower cost, is expected to be helpful for the development of solid electrolyte.
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高影响因子
International Journal of Electrochemical Science
·
2023
·
IF 1.5
Yanhua Zhang,Wenjia Luo,Dongwei Hu,Yuxin Deng,Yuan Chen,Jiadong Deng
Traditional preparation method of solid electrolyte Li 7 La 3 Zr 2 O 12 requires a very long sintering holding time (> 36 hours). A efficient and mass production method, microwave sintering, is utilized to prepared LLZO by which the sintering time is reduced to be 2 ~ 4 h. Results show that cubic phase LLZO can be obtained at 1150 o C ~ 1200 o C. With the increase of holding time from 1 h to 4 h, tetragonal LLZO transforms to cubic which suggests extra thermal energy is generated by coupling dielectric loss with microwave. Pellet sintered with 4 h reaches the highest ionic conductivity of 3.1 x 10 -4 S cm -1 . Long holding time of 6 h will take away a lot of Li from the grain to form excess glass-like phase which is not favorable for conductivity.
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高影响因子
ACS Applied Materials & Interfaces
·
2016
·
IF 7.145
Wenhao Xia,Biyi Xu,Huanan Duan,Yiping Guo,Hongmei Kang,Hua Li,Hezhou Liu
Li7La3Zr2O12 (LLZO) is a promising electrolyte material for all-solid-state battery due to its high ionic conductivity and good stability with metallic lithium. In this article, we studied the effect of crucibles on the ionic conductivity and air stability by synthesizing 0.25Al doped LLZO pellets in Pt crucibles and alumina crucibles, respectively. The results show that the composition and microstructure of the pellets play important roles influencing the ionic conductivity, relative density, and air stability. Specifically, the 0.25Al-LLZO pellets sintered in Pt crucibles exhibit a high relative density (∼96%) and high ionic conductivity (4.48 × 10–4 S cm–1). The ionic conductivity maintains 3.6 × 10–4 S cm–1 after 3-month air exposure. In contrast, the ionic conductivity of the pellets from alumina crucibles is about 1.81 × 10–4 S cm–1 and drops to 2.39 × 10–5 S cm–1 3 months later. The large grains and the reduced grain boundaries in the pellets sintered in Pt crucibles are favorable to obtain high ionic conductivity and good air stability. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy results suggest that the formation of Li2CO3 on the pellet surface is probably another main reason, which is also closely related to the relative density and the amount of grain boundary within the pellets. This work stresses the importance of synthesis parameters, crucibles included, to obtain the LLZO electrolyte with high ionic conductivity and good air stability.
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高影响因子
Journal of Materials Chemistry A
·
2019
·Vol. 7
·期 24
·14565-14574
·
IF 10.733
Yadong Ruan,Yang Lu,Xiao Huang,Jianmeng Su,Changzhi Sun,Jun Jin,Zhaoyin Wen
Solid-state lithium batteries (SSBs) promise high energy and power densities, as well as enhanced safety, owing to the use of Li metal and nonflammable solid-state electrolytes. In particular, cubic garnet-type Ta-substituted Li7La3Zr2O12 (LLZTO) is known for its high ionic conductivity and stability against Li metal. However, poor interfacial contact of the Li/LLZO interface is an obstacle that has come to light in the face of more demanding applications. Herein, to tackle this problem, a novel and facile strategy is demonstrated using H3PO4 to react with the Li2CO3/LiOH passivation layer of the LLZTO surface to form a uniform Li3PO4 modification layer. The Li3PO4 layer not only promotes interfacial wettability by reducing the significant difference of the surface energy, but also produces a robust solid electrolyte interphase (SEI) to inhibit lithium dendrite penetration. The symmetric cell exhibits a dramatically reduced interfacial resistance of 7.0 Ohm cm2 and ultrastable galvanostatic cycling, over 1600 hours at 0.1 mA cm−2 and over 450 hours at 0.5 mA cm−2. Besides this, hybrid solid-state full cells matched with different cathodes also displayed excellent electrochemical performances. LiFePO4 exhibited stable cycling (∼150 mA h g−1) and a good rate performance. In particular, for a S cathode, the coulombic efficiencies remained higher than 99% over 200 cycles. The use of a ternary NCM523 cathode also confirmed the anodic interfacial stability up to high voltage (4.5 V). Therefore, this facile strategy provides a stepping stone for future applications of solid-state Li-ion and Li–S batteries.
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高影响因子
MOLECULES
·
2025
·Vol. 30
·期 9
·2028
·
IF 4.6
Jialu Qu,Xingyu Duan,Ke Xue,Shengli An
Solid-state electrolytes (SSEs) have emerged as the most promising alternative to liquid electrolytes in batteries due to their enhanced stability and safety. Among these, the garnet-type Li7La3Zr2O12(LLZO) solid electrolyte has attracted significant research interest due to its wide electrochemical stability window and good air stability. However, the ionic conductivity of LLZO is lower due to its high sintering temperature and unstable phase structure. In this study, Li6.4+xFe0.2La3Zr2−xBixO12(x = 0, 0.05, 0.1, 0.15) solid electrolytes were synthesized using a conventional solid-state reaction method by co-doping LLZO with Fe3+and Bi3+ions. Compared with pure LLZO, doping with Fe3+effectively stabilizes the cubic phase, thereby enhancing the ionic conductivity. Moreover, Bi3+doping significantly lowers the sintering temperature of the electrolyte, which in turn reduces energy consumption during the processing. The co-doping of Fe3+and Bi3+not only improves the density of the LLZO electrolyte, achieving a relative density of up to 95%, but also increases the ionic conductivity, with a maximum value of 7.57 × 10−4S·cm−1observed at the optimal composition (Li6.4+xFe0.2La3Zr2-xBixO12, x = 0.1).
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高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2021
·
IF 5.316
Yanhua Zhang,Yuxin Deng,Xinglong Gao,Chao Lv,Dawei Luo,Xing Xiang
Solid electrolyte Li 7 La 3 Zr 2 O 12 (LLZO) has received widespread attention due to its excellent comprehensive properties. However, in order to realize its industrial application in all-solid-state lithium batteries, an efficient and low-cost preparation method must be developed. Herein, molten salt method is applied and the effect of sintering temperature , washing solvent and mother powder distribution on the microstructure and properties of LLZO are investigated. Results show that pure cubic LLZO can be obtained at 1250–1300 °C, the lithium loss phase La 2 Zr 2 O 7 is generated at higher temperature of 1330 °C. The Li + conductivity of LLZO obtained at 1300 °C with short time of 80 min reach 2.9 × 10 −4 S cm −1 . Secondly, compared with washing with deionized water, the LiO 4 occupation reduced while the LiO 6 occupation increased when washing with LiOH aqueous, representing an exchange of Li + /H + . The Li + conductivity of LLZO washed with LiOH solution (6.53 × 10 −5 S cm −1 ) is 76% lower than that of deionized water washing (2.73 × 10 −4 S cm −1 ) which due to the excessive Li + concentration. Besides, the Li + conductivity of LLZO (2.57 × 10 −5 S cm −1 ) obtained with mother powder of 2.5 g: 2.5 g is close to one order of magnitude lower than that with 4 g: 1 g (2.23 × 10 −4 S cm −1 ) which is due to too much lithium loss through the upper surface. Excessive mother powder on the upper surface is beneficial to obtain cubic phase LLZO. The molten salt method greatly reduces the mixing time (less than 30 min) and sintering time (80 min) of materials which is an effective and low-cost method to achieve mass production.
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高影响因子
MATERIALS CHEMISTRY AND PHYSICS
·
2022
·
IF 4.778
Tianxiang Ning,Qian Zhang,Piao Liu,Xiangtao Lin,Yinyi Luo,Lidan Liu,Zhiwei Luo,Anxian Lu
In this study, Li 2 O–Ga 2 O 3 -GeO 2 -Gd 2 O 3 (LGGG) glass is doped into Li 7 La 3 Zr 2 O 12 (LLZO) ceramic in proportions of 1, 2, 3, 4, and 5 wt% by a conventional solid-state reaction method. The main crystalline phase that existed in this composite electrolyte is proved to be cubic phase LLZO by XRD patterns. With a dosage of 3 wt% LGGG glass, the composite electrolyte has the highest ionic conductivity of 3.26 × 10 −4 S cm −1 , a maximum relative density of about 96.79%, and minimum activation energy of 0.276 eV at room temperature. This work also verifies that doping the same amount of identified elements into LLZO ceramics in the form of glass can obtain higher ionic conductivity and relative density than in the form of oxides (2.40 × 10 −4 S cm −1 and 92.03%). A symmetric cell composed of this electrolyte reveals a good cycling performance and low overpotential in a total of 230 cycles at a current density of 0.125 mA cm −2 . These results confirm the potential of this LGGG-LLZO composite electrolyte for applicating in new generation all-solid-state lithium-ion batteries.
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Materials Research Express
·
2020
·Vol. 7
·期 2
·025518
·
IF 1.929
Jiali Xue,Kuibao Zhang,Daimeng Chen,Jianjun Zeng,Baozhu Luo
Ta-doped Li7La3Zr2O12 (Ta-LLZO) solid electrolyte ceramics were synthesized by solid-state sintering, spark plasma sintering (SPS) and SPS plus heat-treatment (two-step method) using LiOH·H2O, La2O3, ZrO2 and Ta2O5 as the raw materials. The Ta-LLZO samples prepared from these three routes are all in cubic phase structure. However, the solid-state method results in Ta-LLZO samples with different particle sizes and porous morphology, while the samples prepared by SPS route contain fewer internal voids and smaller particle size. The two-step method not only retains the high compactness of SPS samples, but also the increment of grain size. The SEM results demonstrate that Ta-LLZO sintered by the two-step method shows optimal electrical properties. And the total ionic conductivity is 4.6 × 10−3 S cm−1 at 150 °C and the activation energy is calculated to be 0.38 eV.
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高影响因子
ChemSusChem
·
2018
·Vol. 11
·期 21
·3774-3782
·
IF 7.411
Zhaoshuai Zhang,Long Zhang,Yanyan Liu,Hongqiang Wang,Chuang Yu,Hong Zeng,Li-min Wang,Bo Xu
Graphical The interfacial performance of cubic Li 7 La 3 Zr 2 O 12 (LLZO) as a solid electrolyte for Li-ion batteries is improved by incorporating 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide (BMP-TFSI) ionic liquid. LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811)/Li and LiFePO 4 /Li batteries with the hybrid solid electrolyte exhibit superior cycling stability and low polarization. High grain-boundary resistance, Li-dendrite formation, and electrode/Li interfacial resistance are three major issues facing garnet-based solid electrolytes. Herein, interfacial architecture engineering by incorporating 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide (BMP-TFSI) ionic liquid into a garnet oxide is proposed. The “soft” continuous BMP-TFSI coating with no added Li salt generates a conducting network facilitating Li + transport and thus changes the ion conduction mode from point contacts to face contacts. The compacted microstructure suppresses Li-dendrite growth and shows good interfacial compatibility and interfacial wettability toward Li metal. Along with a broad electrochemical window larger than 5.5 V and an Li + transference number that practically reaches unity, LiNi 0.8 Co 0.1 Mn 0.1 O 2 /Li and LiFePO 4 /Li solid-state batteries with the hybrid solid electrolyte exhibit superior cycling stability and low polarization, comparable to those with commercial liquid electrolytes, and excellent rate capability that is better than those of Li-salt-based ionic-liquid electrolytes.
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PubMed
高影响因子
IONICS
·
2025
·
IF 2.6
Yang Yue,Zhang Zheng,Ma Tianhui,Jia Shaoting,Huang Chao
To achieve high density and high Li-ion conductivity in the garnet LLZO (Li 7 La 3 Zr 2 O 12 ), an effective strategy is to dope it with high-valence elements to stabilize the cubic phase and to lower the sintering temperature. As well known, flash sintering (FS) is characterized by short sintering times and low furnace temperature. Herein, the doping modification of Ta-LLZO by flash sintering at 700 °C for the higher conductivity of LLZO was investigated in the present study. The results indicate that the addition of an appropriate amount of Ta 5+ can enhance the ionic conductivity. The relative density of the sintered cubic Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 is 94.72%, with a corresponding total ion conductivity of 9.8 × 10 –4 S cm −1 , demonstrating good electrical performance. A solid-state lithium metal battery with Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 electrolyte was assembled, and its electrical performance was tested at 50 °C. The results showed that an initial discharge specific capacity of 126.5 mAh g −1 at a 0.1C rate could be reached.
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SOLID STATE IONICS
·
2020
·
IF 3.107
Hong Xu,Xue Zhang,Jianyong Jiang,Ming Li,Yang Shen
Composite polymer electrolyte is promising in future lithium-ion battery due to its high safety, easy-processing feature and electrochemical stability. However, it is still a great challenge to obtain the electrolyte with both low thickness and high conductivity. In this work, we synthesize a ~25 μm thin electrolyte membrane with the Li 7 La 3 Zr 2 O 12 -embedded polyacrylonitrile-based fiber as the 3D backbone and the in-situ polymerized gel electrolyte as the fillers. The electrolyte with the multi-dimensional lithium ion conducting channels exhibits a high conductivity of 1.60 × 10 − 3 S·cm − 1 at 25 °C. The wide electrochemical window of 4.5 V vs. Li/Li + enables the electrolyte to match with high voltage cathode materials. The Li||Li symmetric cell with the electrolyte shows a high cycling stability with more than 350 h at a current density of 0.1 mA·cm − 2 . In addition, the solid-state LiFePO 4 ||Li full cell has a stable charge-discharge cycle at 25 °C. This thin electrolyte can be used in lithium-ion batteries to improve energy density . The method of preparing thin composite polymer electrolyte membrane can also be extended to other polymer-filler systems.
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高影响因子
Nano-Micro Letters
·
2026
·Vol. 18
·期 1
·189
·
IF 36.3
Li Tao,Zhao Guohao,Zhao Zhiyi,Xu Yaqi,Wu Tianli,Peng Dong-Liang,Xie Qingshui,Xu Ying
Li7La3Zr2O12-based electrolytes have got great promise for solid-state lithium (Li) metal batteries because of their high elastic modulus and wide electrochemical stability window. However, the insufficient contact and heterogeneous Li deposition severely hinder their practical applications. Here, a flexible ternary polymethacrylate (PMA) matrix is designed to incorporate with Ta-doped Li7La3Zr2O12 (LLZTO-PMA). The PMA matrix ensures excellent interfacial contact, while the synergistic effects of its polar carbonyl groups and its interaction with LLZTO creating fast interfacial Li+ pathways yield a high ionic conductivity of 0.266 mS cm − 1 at 20 °C. Moreover, the interaction between LLZTO and PMA matrix further guides the formation of a hybrid LiF/Li3N-rich solid electrolyte interphase, which allows a fast Li+ interfacial kinetic due to its lowered Li+ diffusion barrier. Consequently, the LLZTO-PMA electrolyte contributes an ultra-stable Li anode interphase, attaining a lifespan exceeding 10,000 h in symmetric cells and retaining over 96% capacity after 600 cycles in full battery, demonstrating a breakthrough for high-performance solid-state batteries.
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高影响因子
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