JOURNAL OF ALLOYS AND COMPOUNDS
·
2022
·
IF 6.371
Xiyuan Tao,Li Yang,Jiali Liu,Zihao Zang,Peng Zeng,Changfei Zou,Lingguang Yi,Xiaoyi Chen,Xiaolin Liu,Xianyou Wang
Garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) is a promising solid-state electrolyte (SSE) for next generation lithium batteries due to its high Li + conductivity and stability against lithium metal, especially the Li 7−3x Ga x La 3 Zr 2 O 12 (Ga-LLZO) is most valuable because of its high ionic conductivity (> 1 ×10 −3 S cm −1 ). However, it is difficult to prepare high-quality Ga-LLZO by the traditional air ambient sintering. Herein, we develop a simple and efficient rapid ultra-high-temperature sintering (RUHTS) method to prepare high-conductivity Ga-LLZO ceramic SSE. It has been found that the as-prepared Ga-LLZO ceramic SSE with the composition of Li 6.25 Ga 0.25 La 3 Zr 2 O 12 exhibits high relative density of 99%, good ionic conductivity of 1.48 × 10 −3 S cm −1 and large critical current density of 0.5 mA cm −2 after sintering at 1200 °C for 2 min. In addition, the Ga-LLZO SSE shows good electrochemical stability and interfacial compatibility against Li metal. The assembled Li-Li symmetric cell represents a small interfacial impedance of 37 Ω cm 2 . In the same time, the Li/Ga-LLZO/LE+LMNCO full battery has a total impedance of 205 Ω cm 2 , and can deliver a first discharge capacity of 235.1 mAh g −1 at 0.5 C, and the capacity retention rate is 88.3% after 100 cycles. This indicates that the as-prepared Ga-LLZO has good application prospect in the Li-metal solid-state batteries (LMSSBs). Moreover, this method does not require the use of mother powder during preparation process, which will effectively reduce the waste of raw materials, save manufacture costs and be beneficial to quantity production of Ga-LLZO ceramic electrolyte.
研究领域:
材料科学
·
电化学
·
电池技术
✓ 已验证
DOI
高影响因子
Energy Materials
·
2026
·Vol. 6
·期 9
·N
·
IF 11.9
Yuanyuan He\u003Csup\u003E1,\u003C\u002Fsup\u003E,Gengjie Liu\u003Csup\u003E1,\u003C\u002Fsup\u003E,Xin Ao\u003Csup\u003E2,\u003C\u002Fsup\u003E,Bingbing Tian\u003Csup\u003E1,\u003C\u002Fsup\u003E
Solid polymer electrolytes (SPEs) are regarded as ideal solid electrolytes for next-generation lithium-ion batteries due to their high safety, but their low ionic conductivity limits practical applications. The incorporation of garnet-type Lithium Lanthanum Zirconium Oxide (LLZO)-based electrolytes with high Li+ conductivity is an effective strategy to enhance the performance of polyethylene oxide (PEO)-based SPEs. In this study, highly Li+-conductive Ga-doped LLZO (Li6.4Ga0.2La3Zr2O12) was prepared by wet and dry methods, Ga-doped (Ga = 0.2) LLZO is referred to as LLZO for brevity throughout this manuscript, yielding samples denoted as wet-LLZO and dry-LLZO, with abundant and minimal surface residual alkali, respectively. These LLZO nanoparticles with different residual alkali were incorporated as fillers in composite solid polymer electrolytes (CSPEs). Studies demonstrate that the residual alkali, such as Li2CO3, on the LLZO surface effectively disrupts the ordered arrangement of PEO segments, significantly reducing their crystallinity and thus facilitating Li+ transport. Based on this, CSPE with 15 wt% wet-LLZO achieves a high ionic conductivity of 0.80 mS cm-1 and a lithium-ion transference number of 0.36 at 60 °C. The assembled Li/LiFePO4 all-solid-state battery maintains a discharge specific capacity of 142.5 mAh g-1 and a Coulombic efficiency exceeding 99% after 300 cycles at a 1.0 C rate. This work reveals the role of residual surface alkali in the LLZO composite solid electrolyte, providing novel insights for designing high-performance solid-state batteries through filler surface engineering.
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2018
·
IF 8.097
Zhuo Li,He-Ming Huang,Jia-Kun Zhu,Jian-Fang Wu,Hui Yang,Lu Wei,Xin Guo
By dispersing Li6.25Ga0.25La3Zr2O12 (Ga-LLZO) nanoparticles in poly(ethylene oxide) (PEO) matrix, PEO:Ga-LLZO composite polymer electrolytes are synthesized. The PEO: Ga-LLZO composite with 16 vol % Ga-LLZO nanoparticles shows a conductivity of 7.2 × 10–5 S cm–1 at 30 °C, about 4 orders of magnitude higher than the conductivity of PEO. The enhancement of the ionic conductivity is closely related to the space charge region (∼3 nm) formed at the interface between the PEO matrix and the Ga-LLZO nanoparticles. The space charge region is observed by transmission electron microscope (TEM) and corroborated by the phase-field simulation. Using the random resistor model, the lithium-ion transport in the composite polymer electrolyte is simulated by the Monte Carlo simulation, demonstrating that the enhanced ionic conductivity can be ascribed to the ionic conduction in the space charge regions and the percolation of the space charge regions.
研究领域:
材料科学
·
电化学
·
储能
·
固态离子学
✓ 已验证
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
·
2023
·Vol. 34
·期 11
·1-10
·
IF 2.8
Han Linting,Yang Xiaofeng,Wang Hui,Chen Zhiping,Jing Hongxia,Zhang Lixin
As one of the most promising solid electrolytes, Li 7 La 3 Zr 2 O 12 (LLZO) has received great attention in the field of all solid-state lithium-ion batteries. However, LLZO, as a solid material, has far less contact with the electrode than original liquid electrolyte with wettable properties in practical applications. In this study, porous LLZO solid electrolytes were fabricated by both mechanical and dispersive mixing methods with modified kapok fibers as pore-forming agents. The results show that the pores of LLZO prepared by dispersive mixing are more homogeneous than that prepared by mechanical mixing, and the ionic conductivity of LLZO fabricated by dispersive mixing remains in the same order of magnitude as the ionic conductivity of the original LLZO solid electrolyte. At the same time, the formation of ordered pore channels for porous LLZO is conducive to increasing the contact area between the solid electrolyte and the electrode material, which lays a foundation for reducing the impedance of solid electrolyte.
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2019
·
IF 8.456
Yaoyu Ren,Yang Shen,Yuanhua Lin,Ce-Wen Nan
Al-contained Li7–xLa3Zr2–xTaxO12 (xTa-LLZO) powder was synthesized via solid-state reaction, where increasing the Ta doping level was found to reduce the average particle size and facilitate a higher relative density in the sintered pellet. 0.8Ta-LLZO pellets sintered at 1150 °C achieved a relative density of 96.2 ± 0.2% and survived the Li striping/plating test under a unidirectional current polarization of 0.5 mA/cm2 for more than 8 h without short-circuiting. In contrast, other xTa-LLZO sintered pellets with lower Ta doping levels were short-circuited by lithium dendrites after polarization for much shorter time periods. The microstructure of the sintered body played a more essential role in lithium dendrite prevention compared to relative density alone. By characterizing the microstructure of xTa-LLZO sintered pellets, we proposed a formation mechanism of the pathways for lithium dendrite growth.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
ACS Applied Energy Materials
·
2021
·
IF 6.024
Shengdong Tao,Jian Li,Lihua Wang,Weiguo Huang,Minchao Zhang,Zhexi Chi,Shuohan Wang,Yongzhi Chen,Lei Shang
Development of an active filler with a large specific surface area, fast ion conductivity phase, special shape, and high electrochemical stability is a critical issue for prominent performance composite solid-state electrolytes (CSEs) in solid-state lithium-ion batteries. Here, we report large specific surface area and coral-like cubic Li7La3Zr2O12 (LLZO) that was synthesized via a metal–organic framework (MOF) at a low calcination temperature (1000 °C). As active fillers, the coral-like cubic LLZO and lithium oxalyldifluroborate (LiODFB) uniformly distributed in a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix provide an interconnected Li-ion transport channel in CSE, which manifests outstanding properties such as a favorable electrochemical stability window (of 4.85 V vs Li/Li+), high ionic conductivity (1.65 × 10–4 S cm–1, 20 °C), and superior interface compatibility with lithium metal. The assembled LiFePO4/CSE/Li and LiCoO2/CSE/Li cells convey predominate performance and initial specific capacities of 135.0 and 135.9 mA h g–1 at 0.5 C, with capacity retention values of 83.51% after 500 cycles and 93.90% after 200 cycles. The coral-like LLZO with a large specific area reduces polymer crystallinity and provides a large phase interface in CSE through interaction of LLZO with LiODFB and PVDF-HFP. The results suggest that coral-like LLZO prepared by MOFs is a promising filler in CSEs for solid-state lithium-ion batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
PHYSICA STATUS SOLIDI B-BASIC SOLID STATE PHYSICS
·
2026
·Vol. 263
·期 4
·e202500615
·
IF 1.7
Zijian Li,Zihao Wang,Fei Gao,Yuhao Hong,Zhongkai Wu,Wentao Lu,Zihao Huang,Rubin Zhang,Shuqi Fu,Mingyan Jiang,Yong Min,Weiping Zhou,Zhenzhi Cheng,Guangsheng Luo
Garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolytes are among the most promising candidates for all-solid-state lithium batteries owing to their high intrinsic Li + conductivity. However, poor sinterability and unstable Li interfaces hinder practical application. Although Ta/Sr codoping has been employed to stabilize the cubic phase and enhance conductivity, the high cost and sluggish sintering kinetics of Ta limit scalable fabrication. Here, a cost-effective Nb/Sr co-doping strategy is developed to simultaneously promote densification and Li + transport. Sr substitution at La-sites induces transient glassy phases that accelerate sintering and stabilize Li interfaces, achieving an ionic conductivity of 8.8 × 10 −4 S cm −1 and a critical current density (CCD) of 0.65 mA cm −2 . When paired with a LiFePO 4 cathode, the optimized LLSZNO-0.08 (Nb = 0.5, Sr = 0.08) electrolyte delivers 164.8 mAh g −1 with 88% coulombic efficiency at 0.2 C over 150 cycles and retains 140.6 mAh g −1 at 0.5 C with 89% capacity retention. The Nb/Sr co-doped LLZO avoids intentional Al incorporation and achieves stable Li interfacial contact without surface modification. This work correlates structural evolution with ionic transport and interfacial stability, providing mechanistic insight and a scalable route for high-performance LLZO-based electrolytes.
✓ 已验证
DOI
高影响因子
JOURNAL OF THE AMERICAN CERAMIC SOCIETY
·
2017
·Vol. 100
·期 7
·2832-2839
·
IF 2.841
Wenhao Xia,Biyi Xu,Huanan Duan,Xiaoyi Tang,Yiping Guo,Hongmei Kang,Hua Li,Hezhou Liu
Li 7 La 3 Zr 2 O 12 (LLZO) has been reported to react in humid air to form Li 2 CO 3 on the surface, which decreases ionic conductivity. To study the reaction mechanism, 0.5-mol Ta-doped LLZO (0.5Ta–LLZO) pellets are exposed in dry (humidity ~5%) and humid air (humidity ~80%) for 6 weeks, respectively. After exposure in humid air, the formation of Li 2 CO 3 on the pellet surface is confirmed experimentally and the room-temperature ionic conductivity is found to drop from 6.45×10 −4 S cm −1 to 3.61×10 −4 S cm −1 . Whereas for the 0.5Ta–LLZO samples exposed in dry air, the amount of formed Li 2 CO 3 is much less and the ionic conductivity barely decreases. To further clarify the reaction mechanism of 0.5Ta–LLZO pellets with moisture, we decouple the reactions between 0.5Ta–LLZO with water and CO 2 by immersing 0.5Ta–LLZO pellets in deionized water for 1 week and then exposing them to ambient air for another week. After immersion in deionized water, Li + /H + exchange occurs and LiOH H 2 O forms on the surface, which is a necessary intermediate step for the Li 2 CO 3 formation. Based on these observations, a reaction model is proposed and discussed.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2020
·
IF 4.473
Chao Chen,Yao Sun,Linchun He,Masashi Kotobuki,Emil Hanc,Yu Chen,Kaiyang Zeng,Li Lu
The Garnet-type solid electrolyte Li7La3Zr2O12 (LLZO) showing high ionic conductivity and a wide electrochemical potential window is considered as one of the most promising candidates for solid-state batteries. Among various doping derivatives, the Al- and Ga-doped LLZO electrolytes are intensively studied because of their ability to enhance the stability of the cubic structure and to promote good sinter ability as well. Despite showing great similarities in site preference and sintering behavior, the Al and Ga doping derivatives differ by 1 order of magnitude in total ionic conductivity. Therefore, a comparative study on the doping characteristics of Al and Ga with respect to ionic conductivity and sintering behavior is necessary. Herein, we simultaneously introduced Al and Ga into Li sites (AlxGa0.25–x-LLZO) to study their influences on the microstructure and electrochemical properties of LLZO. The results show that Ga doping enables a higher conductivity than Al doping and largely promotes sinter ability at the same time. Compared to Al single doping (Al0.25), Ga-contained compositions (x < 0.25) show significant grain growth. Moreover, a slight inclusion of Ga (Al0.20Ga0.05) not only modifies the sintering behavior that results in a microstructure transition from fine grains of Al0.25 (5–20 μm) to abnormally large grains (several hundred micrometers) but also greatly enhances the conductivity, yielding a value that is 3 times higher. However, further increases in Ga ratio in AlxGa0.25–x results in marginal increases in conductivity. The total conductivity reaches a maximum of 1.19 × 10–3 S cm–1 for Ga single doping (Ga0.25) at room temperature. In addition, Al0.25 also shows fast ion conducting behavior along the grain boundaries with a conductivity of 8.30 × 10–4 S cm–1. Consequently, this study sheds lights on the different doping characteristics between Al and Ga, providing guidance for fine composition engineering of these two promising dopants.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
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).
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
MATERIALS TECHNOLOGY
·
2020
·
IF 1.738
Wei Liu,Fan Deng,Shufeng Song,Guipeng Ji,Ning Hu,Chaohe Xu
Although all-solid-state batteries have good safety and high energy density, they still need to explore high performance solid-state electrolytes to achieve high ionic conductivity, wide electrochemical window and excellent mechanical properties. In this work, we designed a hybrid solid electrolyte to solve these problems via mixing PEO, ionic liquid EmimFSI (1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide), LLZO (Li6.5Mg0.05La3Zr1.6Ta0.4O12) and lithium salt, which aimed at suppression of PEO crystallization and employed to improve the mechanical and electrochemical stability. Accordingly, the LLZO@EmimFSI@PEO derived hybrid solid electrolyte provides an ionic conductivity of 1.0×10-4 S cm-1 at 40oC and electrochemical stability window above 5.0 V vs. Li/Li+. Furthermore, the symmetric cell of Li/hybrid solid electrolyte/Li exhibits flat voltage profiles and stable lithium plating/stripping process, a solid-state battery based on the hybrid solid electrolyte combined with high-energy lithium metal anode and NCM622 (LiNi0.6Co0.2Mn0.2O2) cathode was also demonstrated.
✓ 已验证
DOI
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.
研究领域:
材料科学
·
固态电池研究
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）