CERAMICS INTERNATIONAL
·
2017
·Vol. 43
·期 17
·15805-15810
·
IF 2.986
Lixiong Bai,Wendong Xue,Yan Li,Xiaoguang Liu,Yong Li,Jialin Sun
The surface structure and interfacial behaviour of Al-Li 7 La 3 Zr 2 O 12 were studied by Rietveld refinement of X-Ray Diffraction(XRD), Raman Spectra and Electrochemical Impedance Spectroscopy . It was found that Li + with different amount in Li-O octahedra on the surface of Al-Li 7 La 3 Zr 2 O 12 affects the electrochemical behaviour of the material. The increase of Li + occupancy in octahedral site can reduce the activation energy on the surface and improve the ionic conductivity of the material.
研究领域:
材料科学
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固态化学
·
电化学
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高影响因子
CERAMICS INTERNATIONAL
·
2020
·Vol. 46
·期 8
·10917-10924
·
IF 3.83
Li Yang,Qiushi Dai,Lei Liu,Dingsheng Shao,Kaili Luo,Sidra Jamil,Hong Liu,Zhigao Luo,Baobao Chang,Xianyou Wang
Solid electrolytes could address the increasingly urgent safety and energy density concerns of lithium-ion batteries. Among several kinds of solid electrolytes, Ta-doped Li 7 La 3 Zr 2 O 12 (Ta-LLZO) became a research hotspot because of its high Li-ion conductivity and chemical stability against Li-metal and air. However, the preparation of high quality LLZO ceramic electrolyte via conventional air ambient sintering method is still a big challenge due to the serious “Li-loss” and abnormal grain growth phenomenon during the long-time high-temperature sintering process . Herein, a new rapid ultra-high-temperature air ambient sintering method without mother powder (MP) is put forward for the preparation of high quality Ta-LLZO ceramic electrolyte. The rapid sintering strategy can effectively restrain “Li-loss”. Furthermore, it is demonstrated that the none-mother-powder method is superior to traditional mother-powder method. Ta-LLZO ceramics sintered without MP via this rapid sintering method own small grain size, tight grain boundary, dense microstructure and high conductivity. Specifically, the Ta-LLZO ceramic sintered at 1360 °C for 10 min without MP exhibits high conductivity (8.5 × 10 −4 S cm −1 at 25 °C) and high relative density (97%), which equate those made by hot pressing sintering method. Without MP, the sintering process can avoid a lot of material waste and simplify the operation process. Moreover, the rapid sintering process can sharply shorten sintering time and reduce energy consumption. Therefore, this low-cost high-efficient sintering strategy can be effectively used in the large-scale production of high-quality Ta-LLZO ceramic electrolyte.
研究领域:
材料科学
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固态离子学
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能源材料
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电化学
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无机非金属材料
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电池技术
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高影响因子
SOLID STATE IONICS
·
2013
·
IF 2.046
Alexandre Dumon,Mian Huang,Yang Shen,Ce-Wen Nan
Strontium doped lithium ion garnets Li 7 La 3 Zr 2 O 12 (LLZ) with 0.9 wt% to 8.4 wt% content of added Sr were synthesized via conventional solid-state reaction. X-ray diffraction patterns confirmed the cubic garnet structure of the sintered samples. A small amount of strontium was substituted to lanthanum in LLZ lattice. Further analysis showed SrCO 3 acted as a sintering aid for cubic LLZ ceramics and significantly increased the grain size of the sintered pellets. A conductivity of 2.10 × 10 − 4 S/cm at 297 K was obtained for the undoped LLZ. The total ionic conductivity reached a maximum of about 5 × 10 − 4 S/cm at 297 K with an activation energy of about 0.31 eV for 1.7 wt% Sr added LLZ sintered for 20–24 h in alumina crucible.
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高影响因子
ACS Applied Materials & Interfaces
·
2018
·
IF 8.097
Xiao Huang,Yang Lu,Jun Jin,Sui Gu,Tongping Xiu,Zhen Song,Michael E. Badding,Zhaoyin Wen
Li-garnet Li7La3Zr2O12 (LLZO) is a promising candidate of solid electrolytes for high-safety solid-state Li+ ion batteries. However, because of its high reactivity to water, the preparation of LLZO powders and ceramics is not easy for large-scale amounts. Herein, a method applying water-based solvent is proposed to demonstrate a possible solution. Ta-doped LLZO, that is, Li6.4La3Zr1.4Ta0.6O12 (LLZTO), and its LLZTO/MgO composite ceramics are made by attrition milling, followed by a spray-drying process using water-based slurries. The impacts of parameters of the method on the structure and properties of green and sintered pellets are studied. A relative density of ∼95%, a Li-ion conductivity of ∼3.5 × 10–4 S/cm, and uniform grain size LLZTO/MgO garnet composite ceramics are obtained with an attrition-milled LLZTO/MgO slurry that contains 40 wt % solids and 2 wt % polyvinyl alcohol binder. Li–sulfur batteries based on these ceramics are fabricated and work under 25 °C for 20 cycles with a Coulombic efficiency of 100%. This research demonstrates a promising mass production method for the preparation of Li-garnet ceramics.
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PubMed
高影响因子
Journal of Advanced Ceramics
·
2022
·Vol. 11
·期 10
·1530-1541
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IF 11.534
Zhang Chang,Hu Xiangchen,Nie Zhiwei,Wu Cong,Zheng Nan,Chen Shaojie,Yang Yihang,Wei Ran,Yu Jiameng,Yang Nan,Yu Yi,Liu Wei
Garnet-type oxide is one of the most promising solid-state electrolytes (SSEs) for solid-state lithium-metal batteries (SSLMBs). However, the Li dendrite formation in garnet oxides obstructs the further development of the SSLMBs seriously. Here, we report a high-performance garnet oxide by using AlN as a sintering additive and Li as an anode interface layer. AlN with high thermal conductivity can promote the sintering activity of the garnet oxides, resulting in larger particle size and higher relative density. Moreover, Li 3 N with high ionic conductivity formed at grain boundaries and interface can also improve Li-ion transport kinetics. As a result, the garnet oxide electrolytes with AlN show enhanced thermal conductivity, improved ionic conductivity, reduced electronic conductivity, and increased critical current density (CCD), compared with the counterpart using Al 2 O 3 sintering aid. In addition, Li symmetric cells and Li∣LiFePO 4 (Li∣LFP) half cells using the garnet electrolyte with the AlN additive exhibit good electrochemical performances. This work provides a simple and effective strategy for high-performance SSEs.
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高影响因子
CERAMICS INTERNATIONAL
·
2021
·Vol. 47
·期 16
·22768-22775
·
IF 4.527
Libin Zhuang,Xiao Huang,Yang Lu,Jiawen Tang,Yongjian Zhou,Xin Ao,Yan Yang,Bingbing Tian
Cubic phase garnet-type Li 7 La 3 Zr 2 O 12 (LLZO) is a promising solid electrolyte for highly safe Li-ion batteries. Al-doped LLZO (Al-LLZO) has been widely studied due to the low cost of Al 2 O 3 . The reported ionic conductivities were variable due to the complicated Al 3+ -Li + substitution and Li x AlO y segregation in Al-LLZO ceramics. This work prepared Li 7−3 x Al x La 3 Zr 2 O 12 ( x = 0.00~0.40) ceramics via a conventional solid-state reaction method. The AC impedance and corresponding distribution of relaxation times (DRT) were analyzed combined with phase transformation, cross-sectional microstructure evolution , and grain boundary element mapping results for these Al-LLZO ceramics to understand the various ionic transportation levels in LLZO with different Al-doping amounts. The low conductivity in low Al-doped (0.12~0.28) LLZO originates from the slow Li + ion migration (1.4~0.25 μs) in the cubic-tetragonal mixed phase. On the other hand, LiAlO 2 and LaAlO 3 segregation occur at the grain boundaries of high Al-doped (0.40) LLZO, resulting in a gradual Li + ion jump (6.5 μs) over grain boundaries and low ionic conductivity. The Li 6.04 Al 0.32 La 3 Zr 2 O 12 ceramic delivers the optimum Li + ion conductivity of 1.7 × 10 −4 S cm −1 at 25 °C.
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高影响因子
Energy Storage Materials
·
2022
·
IF 20.831
Hongpeng Zheng,Guoyao Li,Jiqiong Liu,Shaoping Wu,Xingmin Zhang,Yongmin Wu,Hong Zhu,Xiao Huang,Hezhou Liu,Huanan Duan
Lithium-stuffed garnets , one of the most promising solid electrolytes for all-solid-state lithium batteries (ASSLBs), are typically vulnerable to water or moisture. In this work, Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLZT) with ionic conductivity of 7.36 × 10 −4 S cm −1 at room temperature and ultrahigh moisture stability is designed and synthesized by a solvent-free route with no excess lithium source. After storing in ambient atmosphere for four months, the LLZT maintains an ionic conductivity of 6.41 × 10 −4 S cm −1 . With optimized lithium contents, the LLZT is stored in an atmosphere rich in H 2 O and CO 2 at 65°C for 24 hours and the ionic conductivity only decreases by 6.9% to 6.6 × 10 −4 S cm −1 . Even undergone water-immersion, the LLZT pellet shows good electrochemical stability, which allows an interfacial resistance of 14.6 Ω cm 2 with Li and stable cycling performance of Li|LLZT|LFP cell, exhibiting a high capacity retention of 93% after 100 cycles. Several important features including high relative density, few grain boundaries, water-stable secondary phase of La 2 Zr 2 O 7 , and the Li + -deficient garnet lattice are combined to contribute to the moisture stability as suggested by morphology and surface chemistry analysis and first-principles calculations. This study provides valuable insights into synthesizing fast and moisture-stable lithium garnets in a time-efficient way, which is vital for developing garnet-based ASSLBs.
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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.
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高影响因子
ELECTROCHIMICA ACTA
·
2015
·
IF 4.504
Yiqiu Li,Zheng Wang,Yang Cao,Fuming Du,Cheng Chen,Zhonghui Cui,Xiangxin Guo
W-doped Li 7 La 3 Zr 2 O 12 electrolytes with composition of Li 7-2x La 3 Zr 2-x W x O 12 (LLZWO, x = 0-0.55) were prepared by conventional solid state reaction. The incorporation of W proves beneficial to stabilization of cubic phase and densification of the ceramic, resulting in relative density of 96% and ionic conductivity of 6.6 × 10 −4 S cm −1 at 25 °C. Further analysis indicates that the LLZWO is not only chemically but also electrochemically (at least up to 4.5 V) stable against Li metal anodes. The batteries consisting of Li/LLZWO/Electrolyte-soaked separator/LiNi 0.33 Mn 0.33 Co 0.33 O 2 at 25 °C exhibit the capacity of 142 mAh g −1 at a constant current of 15 mA g −1 at the first discharge, which could run for 20 cycles with capacity retention of 94%. These results indicate that the W-doped LLZO ceramics are promising electrolytes for solid state lithium ion batteries.
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高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2023
·
IF 4.5
Baoxiang Huang,Hongying Hou,Xiaohua Yu,Jian Lan,Bin Liu,Songlin Tan,Xianxi Liu
Inorganic/organic composite solid electrolytes are receiving the ever-increasing attention due to high safety and flexibility, however, inferior organic/inorganic interface compatibility also leads to the serious agglomeration of ceramic particles and severe blockage of Li + transport. Grafting amphoteric sulfonate betaine (SB) onto the surfaces of inorganic/organic components could act as the “wielding flux” and the ion-conductive interface layer, thus resulting in a homogeneous dispersion of the inorganic components, high interface compatibility and ionic conductivity. Herein, a series of composite solid electrolytes were prepared by scraping method, in which SB-modified PVDF (SB-PVDF) acted as the ion-conductive polymer matrix and combined with SB-modified Li 7 La 3 Zr 2 O 12 (SB-LLZO) with the different contents (0%, 10%, 20%, 30% and 40%) and 20% bis(trifluoromethane) sulphonyl lithium (LiTFSI). The resultant composites were marked as 0 % SB-LLZO/SB-PVDF/LiTFSI, 10 %SB-LLZO/SB-PVDF/LiTFSI, 20 %SB-LLZO/SB-PVDF/LiTFSI, 30 %SB-LLZO/SB-PVDF/LiTFSI and 40 %SB-LLZO/SB-PVDF/LiTFSI, respectively. Desirably, 30 %SB-LLZO/SB-PVDF/LiTFSI exhibited high ionic conductivity of 1.95 × 10 -4 S/cm, high Li + transference number (t Li + ) of 0.71 and wide electrochemical stability window of 5.31 V. Furthermore, the corresponding Li//30 %SB-LLZO/SB-PVDF/LiTFSI//LiFePO 4 cell delivered the reversible discharge capacity of 136.9 mAh/g and capacity retention of 95.1% after 200 cycles at 1.0 C. Seemingly, such a double-surface-modification structural design of the composite solid electrolyte showed the promising potential for solid state lithium ion batteries.
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高影响因子
SOLID STATE IONICS
·
2014
·
IF 2.112
Ru-Jun Chen,Mian Huang,Wen-Ze Huang,Yang Shen,Yuan-Hua Lin,Ce-Wen Nan
Li 7 La 3 Zr 2 O 12 (LLZ) ceramics with a garnet-type structure were prepared via the conventional solid-state reaction through different calcining processes. The calcining time and temperature were investigated. The results showed that the ionic conductivity of LLZ samples at room temperature decreased as the calcining temperature increased. The highest conductivity of 2.48 × 10 − 4 S cm − 1 was obtained for the sample with the calcining process at 900 °C. The amount of doping Al was also investigated, which showed different effects depending on the calcining process.
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高影响因子
SOLID STATE IONICS
·
2018
·
IF 2.751
Xing Xing Pan,Jian Xin Wang,Xiao Hui Chang,Ya Dong Li,Wan Bing Guan
A solid-liquid composite method (SLM) of Al-substituted cubic lithium lanthanum zirconium garnet (c-LLZO) was developed. Cubic LLZO powders whose composition was Li 6.23 Al 0.26 La 3 Zr 1.88 O 11.76 were prepared from the stoichiometric mixtures of lithium acetate , lanthanum oxide, zirconia and alumina , followed by an annealing of the dried precursor at 750 °C for 12 h in an air atmosphere. The resultant powders were characterized by XRD , SEM and ICP-OES. The conventional solid-state reaction methods using carbonates and hydroxides as lithium sources are also simply introduced as a comparison. In addition, the phase formation of c-LLZO powders synthesized by the ZrO 2 powders with different specific surfaces as raw material was also investigated. The results show that the cubic garnet phase LLZO powders was obtained when the value of the specific surface area (SSA) of the material ZrO 2 powder was about 110 m 2 g − 1 . Sintering these cubic phase powders at 1150 °C for 6 h in air after uniaxial pressing obtained a dense ceramic pellet with a relative density of 91.2% and ionic conductivity of 2.54 × 10 − 4 S cm − 1 at 23 °C.
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高影响因子
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