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.
研究领域:
材料科学
·
能源存储与转换
✓ 已验证
DOI
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.
研究领域:
材料科学
·
电化学
·
能量存储
✓ 已验证
DOI
高影响因子
SOLID STATE IONICS
·
2022
·
IF 3.699
Tianxiang Ning,Yanzhi Zhang,Qian Zhang,Xuefeng Shen,Yinyi Luo,Taoyong Liu,Piao Liu,Zhiwei Luo,Anxian Lu
In this study, Ta single-doped Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (Ta 0.6 ) and a series of Ta, Sr co-doped Li 6.4+x La 3-x Sr x Zr 1.4 Ta 0.6 O 12 (Ta 0.6 Sr x , x = 0.1, 0.2, 0.3, and 0.4) electrolytes are synthesized via a two-step process. The XRD result reveals that all samples have a pure cubic phase, which indicates that Ta 5+ and Sr 2+ can enter the lattice of LLZO and stabilize the cubic phase. The SEM images exhibit that all samples have a dense microstructure and tight grain boundary without obvious holes. The excellent properties are achieved when the doping amount of Sr reaches 0.2 mol. Among all designed samples, the Ta 0.6 Sr 0.2 has the highest Li + conductivity and relative density of 8.54 × 10 −4 S cm −1 and 98.79%, respectively, as well as the lowest activation energy roughly 0.302 eV. Additionally, the symmetrical cell's galvanostatic cycling data show that it has excellent cycling performance and extremely low overpotentials even after 350 cycles, indicating that it can be successfully applied to next-generation all-solid-state lithium-ion batteries (ASSLIBs).
研究领域:
材料科学
·
电化学
·
能量存储
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2022
·
IF 16.744
Jingtao Wang,Shiyuan Guo,Zhenghua Li,Weijie Kou,Jiachen Zhu,Jingchuan Dang,Yafang Zhang,Wenjia Wu
To achieve high energy density of all-solid-state lithium batteries, solid-state electrolytes (SSEs) are required to be thin and highly conductive. Although constructing efficient inorganic Li-ion transfer network can provide excellent conductivity for SSEs, it is still challenging for these SSEs to simultaneously realize thin thickness and mechanical stability. Herein, well-ordered vertical Li 7 La 3 Zr 2 O 12 sheet arrays (VLSA) were prepared, followed by introducing triple-layer ion-conducting polymers to fabricate 8 μm-thick VLSA composite solid electrolyte (CSE). We demonstrate that vertical and short VLSA (major path, accounting for 71.4% of Li-ion transfer) and VLSA/polymer interface (minor path, 27.8%) contribute to the high ionic conductivity of 2.60 × 10 −4 S cm −1 and ionic conductance of 0.5 S at 30 °C, ranking one of the highest values among reported SSEs. The stiff VLSA enhances the mechanical strength of CSE, while the polymer existing in VLSA channels serves as a deformable buffer, endowing CSE with bendable property. Besides, the trilayer polymer structure permits this electrolyte to be compatible with lithium anode and high-voltage cathode. Therefore, the high-loading LiNi 0.5 Co 0.2 Mn 0.3 O 2 (NCM523) cell can be cycled with limited lithium anode (N/P ratio = 1.18) over 158 cycles with capacity retention upon 80%, realizing a high energy density of 458.4 Wh kg −1 .
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2013
·
IF 3.777
Mian Huang,Wei Xu,Yang Shen,Yuan-Hua Lin,Ce-Wen Nan
Ge-doped Li 7 La 3 Zr 2 O 12 (LLZ) is prepared via the conventional solid-state reaction. Our results showed that doping Ge of less than 1 wt% could stabilize the cubic phase of garnet-type LLZ and also increase its ionic conductivity up to 8.28 × 10 −4 S/cm at room temperature . When the content of Ge dopant is higher, GeO 2 impurity phase would appear and there coexists cubic and tetragonal mixed structures, lowering the conductivity. By combining X-ray absorption near-edge spectroscopy and full multiple-scattering theory, we find that Ge more likely enters into the Li and La crystallographic sites instead of the Zr site, which provides understanding of the micro-structural modulation by Ge dopants and the subsequent enhancement in the ionic conductivity.
研究领域:
材料科学
·
固体化学
·
光谱学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2018
·
IF 3.779
Xiaolan Chen,Tian Wang,Wanzheng Lu,Tianxiang Cao,Mingzhe Xue,Bing Li,Cunman Zhang
A modified solution method was applied to synthesize cubic garnet solid-state electrolyte Li 7 La 3 Zr 2 O 12 (LLZO) and Li 6.45 Ca 0.05 La 2.95 Ta 0.6 Zr 1.4 O 12 (LCLTZO). The synergetic doping of Ca and Ta is found to induce the formation of cubic LCLZTO with high ionic conductivity of 4.03 × 10 −4 S cm −1 while LLZO without substitution exhibits tetragonal phase with low conductivity. A Li-S cell with sulfur cathode and as-prepared LCLTZO solid electrolyte “separator” was conducted to deliver large initial discharge capacity of 1090 mAh g −1 with high initial Coulombic efficiency up to 92%. Cell with LCLTZO also exhibited better cycling performance at 0.2 C and extremely high Coulombic efficiency (close to 100%) than the cell without solid electrolyte. Better rate performance was also achieved at lower rate (0.2 C, 0.5 C and 1 C) by cell with LCLTZO although it lost advantages at higher rate of 2 C and 5 C due to the limitation of ionic conductivity of LCLTZO. Energy dispersive X-ray spectroscopy (EDS) provided direct evidence that LCLTZO solid electrolyte greatly suppressed the shuttle effect generated by polysulfides . The electrochemical impedance spectroscopy was applied to discuss the difference between cells with and without LCLTZO during the discharge process. Charge transfer reaction referred to soluble polysulfides was found to be slower in cell with LCLTZO than that in cell without solid electrolyte.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
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
·
无机非金属材料
·
电池技术
✓ 已验证
DOI
高影响因子
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
·
固态化学
·
电化学
✓ 已验证
DOI
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.
研究领域:
材料科学
·
固态离子学
✓ 已验证
产品关联
DOI
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.
研究领域:
材料科学
·
能源技术
✓ 已验证
产品关联
DOI
PubMed
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.
✓ 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
危险品化学品经营许可证（带存储）