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.
研究领域:
材料科学
·
固态电池研究
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2017
·
IF 4.798
Fei Chen,Dunjie Yang,Wenping Zha,Bodi Zhu,Yanhua Zhang,Junyang Li,Yuping Gu,Qiang Shen,Lianmeng Zhang,Donald R. Sadoway
The advantages of all-solid-state batteries in terms of high energy density and improved safety have accelerated the research into durable and reliable solid electrolytes and into scale up of their processing technology. High lithium-ion-conducting Li 7 La 3 Zr 2 O 12 (LLZO) ceramic-based solid electrolytes have been intensively studied recently, but their widespread commercial deployment has been constrained due to their fragility and brittleness . In the present study, LLZO ceramic powders have been successfully incorporated into the polyethylene oxide (PEO) polymer by tape casting. The ionic conductivity of the PEO/LLZO composite electrolyte membranes is significantly enhanced at the optimal LLZO concentration of 7.5 wt.% at which the materials exhibits maximum ionic conductivity of 5.5 × 10 −4 S·cm −1 at 30 °C. The ionic conductivity enhancement mechanism of the composite electrolyte is revealed by differential scanning calorimetry (DSC), which shows that the LLZO filler represses crystallinity in PEO. Furthermore, as evidence of the advantageous electrochemical properties of the composite electrolyte an all-solid-state battery of LiFePO 4 /Li fabricated herein delivered a maximum discharge capacity of 150.1 mAh·g −1 at 0.1C, good cycling performance, and excellent rate capability under 60 °C.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
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.
研究领域:
材料科学
·
能源技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2022
·
IF 6.371
Yanhua Zhang,Xinglong Gao,Zijun Tang,Yuhang Mei,Xing Xiang,Jiadong Deng
The lithium dendrites growth in Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolytes has severely restricted the development of all-solid-state lithium batteries. Herein, two different dynamic properties interlayers of electronically conductive Al and an electronically non-conductive Al 2 O 3 are constructed at the Li/LLZO interface, and the lithium dendrite growth mechanism is explored. Results show that battery with Al interlayer occur internal short circuit in 95 cycles, while the battery with annealed Al 2 O 3 interlayer has good cycle stability of 1000 cycles with polarization voltage below 0.1 V. Besides, dendritic lithium dendrites can be clearly observed at the LLZO grain boundaries of battery with Al interlayer. Raman and XPS results show that the Al 2 O 3 interlayer reacts with Li + during the charge and discharge process to form a Li-Al-O compound which is Li + conductive. It is concluded that the lithium dendrite inhibition mechanism of the Li-Al-O compound interlayer is that it can promote the Li + conduction from LLZO to lithium anode to undergo a lithium deposition reaction, and prevents electrons from conducting to LLZO and combine with Li + to occur lithium dendrite growth. While for the Al interlayer, electrons can reach LLZO through the interlayer to combine with Li + thus occurring the lithium dendritic growth.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
SOLID STATE IONICS
·
2019
·
IF 2.886
Daoguang Zheng,Jianfeng Zhang,Qin Wang,Xingxing Pan,Jianxin Wang,Wanbing Guan,Jun Yang
Polycrystalline cubic Li 6.5 Al 0.22 La 3 Zr 1.93 O 11.94 (LLZO) with garnet structure has been synthesized by solid-liquid method (SLM) with acrylic acid as organic complexing agent , and acetate sol coated nano-ZrO 2 powders as template. The polymeric precursors are characterized by means of TG/DTA, the resultant powders and sintered LLZO pellets are characterized by ICP-OES, X-ray diffraction (XRD), scanning electron microscopy (SEM) and impedance spectroscopy . It is shown that the morphology of the powders is dependent on the preparation conditions such as molar ratio of acrylic acid to metallic ions (L/M) and the pH values. Prepared powders are purity, single phase, an ellipsoidal shape and a particle size of 2–4 μm with good neck connection. The ionic conductivity of sintered LLZO pellets at 1100 °C for 6 h at room temperature is 3.09 × 10 − 4 S cm − 1 and the relative density is 94.1%. The solid-liquid method can lower the sintering temperature , greatly shortens holding time, and gets relatively good the ionic conductivity and it is suitable for mass synthesis of high performance LLZO powders with the advantages of less amount of organic reagent and friendly environment.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CERAMICS INTERNATIONAL
·
2016
·
IF 2.758
Zhongli Hu,Hongdong Liu,Haibo Ruan,Rong Hu,Yongyao Su,Lei Zhang
Li 7 La 3 Zr 2 O 12 (LLZO) has cubic garnet type structure and is a promising solid electrolyte for next-generation Li-ion batteries. In this work, Al-doped LLZO was prepared via conventional solid-state reaction. The effects of sintering temperature and Al doping content on the structure and Li-ion conductivity of LLZO were investigated. The phase composition of the products was confirmed to be cubic LLZO via XRD . The morphology and chemical composition of calcined powders were investigated with SEM, EDS , and TEM . The Li-ion conductivity was measured by AC impedance. The results indicated the optimum sintering temperature range is 800–950 °C, the appropriate molar ratio of LiOH·H 2 O, La(OH) 3 , ZrO 2 and Al 2 O 3 is 7.7:3:2:(0.2–0.4), and the Li-ion conductivity of LLZO sintered at 900 °C with 0.3 mol of Al-doped was 2.11×10 −4 S cm −1 at 25 °C.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
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.
研究领域:
材料科学
·
能源存储与转换
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2026
·
IF 5.5
Yangli Chen,Delin Sun,Hailong Zhu,Yaqi Hou,Huaiyang Zuo,Shumin Zheng,Jing Wang,Shiming Yang,Bao Wang
Garnet-type Li7La3Zr2O12 (LLZO) stands out as one of the most promising ceramic materials for solid-state lithium-ion batteries (LIBs), owing to its high ionic conductivity and electrochemical stability. However, critical challenges such as high interfacial resistance and poor cycling performance, particularly at subzero temperatures, have hindered its widespread application. Herein, we propose a composite solid electrolyte design by dispersing Eu-doped Li7+xLa3Zr2-xEuxO12 as an inorganic filler into a gel polymer matrix based on poly-1,3-dioxolane. This inorganic-polymer hybrid structure significantly enhances the low-temperature performance of LIBs. The incorporation of the gel polymer not only improves the interfacial contact between LLZO and the electrodes but also provides multiple pathways for lithium-ion transport, leading to enhanced ionic conductivity with the value of 5.6 × 10–4 S cm–1 at 20 °C and 9.34 × 10–5 S cm–1 at −20 °C. Electrochemical evaluations demonstrate that the LLZEO/PDL composite electrolyte exhibits remarkable performance at −20 °C: Li|Li symmetric cells achieve stable cycling for over 2000 h at 0.1 mA cm–2, and Li|LiFePO4 full cells deliver a high reversible capacity of 71.8 mAh g–1 at 0.1C, with a capacity retention of 68.8% after 300 cycles.
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2019
·
IF 0
Yun Zhao,Jianhua Yan,Weiping Cai,Yimei Lai,Jun Song,Jianyong Yu,Bin Ding
Ceramic Li 7 La 3 Zr 2 O 12 is one of the most attractive electrolyte materials for solid-state batteries due to its high ionic conductivity and chemical/thermal stability, but the battery performance is always limited by the high electrolyte-electrode interfacial resistances. Here, we have fabricated elastic solid electrolytes by filling ionic-conductive polymers into well-aligned Li 6.4 La 3 Zr 2 Al 0.2 O 12 (LLZO) nanofiber films. Such electrolytes can provide fast and continuous ionic-transportation channels and thus exhibit a high ionic conductivity of 1.16 × 10 −4 S cm −1 at 30 °C. Moreover, the elastic surfaces of the electrolytes can well conform to electrodes without separations to adapt volume changes of the electrodes during the repeated cycles, enabling a stable Li plating/stripping cycling over 700 h. Fabricated solid-state NCA//Li cells exhibit ultra-low internal resistances of 87 Ω and deliver large discharge capacities with high Coulombic efficiencies that are comparable with the liquid type batteries. The reported approach allows low-cost fabrication of solid electrolytes that possess high ionic conductivity for solid state batteries .
研究领域:
材料科学
·
储能技术
·
电化学
·
纳米材料
·
固态电池
✓ 已验证
DOI
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.
研究领域:
材料科学
·
能源技术
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2022
·
IF 6.959
Yixuan Guo,Jun Cheng,Zhen Zeng,Yuanyuan Li,Hongqiang Zhang,Deping Li,Lijie Ci
Garnet-type Li7La3Zr2O12 (LLZO) has been widely used as a filler in composite solid electrolytes (CSEs) to achieve high-performance solid-state batteries (SSBs). Unfortunately, moisture-sensitive LLZO suffers from surface Li2CO3 passivation when being exposed to an ambient atmosphere. The insulated Li2CO3 layer is thought to reduce the Li+ transportability of CSEs. However, further studies are still needed to find out the underlying mechanism, which helps to guide future filler modification and electrolyte design. Herein, the role of the Li2CO3 layer in CSEs is elucidated from different perspectives. The passivate Li2CO3 layer is verified to prohibit the formation of the high conductive interlayer, change the Li+ transport pathway, and decrease the carrier concentration in CSEs. Also, the Li2CO3 layer would reduce the electropositivity of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) particles, which therefore weakens the anchoring effect toward bis(trifluoromethanesulfonyl)imide (TFSI)−. Accordingly, without Li2CO3, the electrolyte of polyethylene oxide/LiTFSI/IL (ionic liquid) with LLZTO-AT (PLILA) displays 2 times higher ionic conductivity and an improved Li+ transference number of 0.49. Additionally, an excellent cycling performance is presented in Li symmetric cells and full cells with PLLA. This work provides a novel perspective for future research on lithium-ion transport mechanisms and inspires designing better-performance SSBs.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
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.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）